Co3O4纳米阵列的制备及应用
朱红林，郑岳青*
（宁波大学 化学合成与绿色应用研究所 浙江 宁波 315211）
摘要：Co3O4纳米阵列因其特有的性质、丰富的3D结构、多样的形貌、独特的表面界面效应和良好的稳定性等在能量转换与存储、光电催化、气体传感等诸多领域中具有广泛的应用前景而得到广泛研究。对近年来有关Co3O4纳米阵列的制备方法、及其阵列材料在电催化分解水、能量存储与转换、电催化氧还原、光电催化二氧化碳还原、气体传感、一氧化碳氧化、非酶电催化葡萄糖、电磁吸收、疏水分离及有机物降解等研究领域的应用进行了综述。最后，对Co3O4纳米阵列发展过程中尚待解决的问题进行了总结，并对其未来的发展方向进行了展望。
关键词：Co3O4纳米阵列；纳米材料；能量存储材料；能量转换材料；电极材料
中图分类号：O614.8 文献标识码：A 文章编号：0258-3283（2019）--
Preparation and Application of Co3O4 Nanoarrays Zhu Hong-lin, Zheng Yue-qing* (Chemistry Institute for Synthesis and Green Application, Ningbo University, Ningbo, 315211, China), Huaxue Shiji, 2019, 41(11), ～
Abstract：The Co3O4 nanoarrays, possessing unique surface interfacial effect, rich and various morphologies, good stability, have attracted intensive research interest in many fields such as energy storage, photoelectrocatalysis and gas sensors. Some methods for preparing Co3O4 nanoarrays are summarized in recent years. In addition, it also summarized the applications of Co3O4 nanoarrays in the field such as water electrolysis, energy storage and conversion, oxygen reduction reaction, gas sensing materials, photo/electrochemical reduction of CO2, CO oxidation, nonenzymatic electrocatlysis for glucose, electromagnetic materials, hydrophobic separation materials and removal of volatile organic compounds. Finally, the problems remaining to be solved are summarized, and the future development and research direction of Co3O4 nanoarrays are outlined.
Key words：Co3O4 nanoarrays; nanomaterials; energy storage materials; energy conversion materials; electrode materials
引用本文:朱红林，郑岳青. Co3O4纳米阵列的制备及应用. 化学试剂, 2019, 41(11): 1101-1109.
Co9S8-CuS纳米片阵列的电沉积制备及其
电催化产氧性能研究
郭芬岈a，马雨涵b，戎怡珅b，黎挺挺*a
（宁波大学a. 材料科学与化学工程学院，b. 医学院，浙江 宁波 315211）
摘要：过渡金属硫化物因其制备简单、导电性好以及具有丰富的氧化还原性质被广泛用作电催化剂。在导电基底上原位生长复合材料被认为可有效提高催化剂的电催化性能。基于此，利用简单、可控的电沉积法，以泡沫铜作为导电基底，以硝酸铜和硝酸钴作为铜源和钴源原位制备了Co9S8-CuS纳米片阵列。在三电极体系中，将Co9S8-CuS纳米片阵列作为阳极在1 mol/L KOH溶液中得到了优异的电催化析氧性能，Co9S8-CuS纳米片阵列获取50 mA/cm2电流密度所需的过电位仅为370 mV，其Tafel斜率低至108 mV/dec，其优异的电催化析氧性能归因于较大的催化活性面积以及复合材料中Co9S8与CuS之间的协同作用。
关键词：电催化；析氧反应；电沉积；Co9S8-CuS；协同作用
中图分类号：O643.36 文献标识码：A 文章编号：0258-3283（2019）--
Electrodeposition of Co9S8-CuS Nanosheet Arrays for Electrocatalytic Oxygen Evolution Reaction Guo Fen-yaa, Ma Yu-hanb, Rong Yi-shenb, Li Ting-ting*a (a. School of Material Science and Chemical Engineering, b. Medical School, Ningbo University, Ningbo 315211), Huaxue Shiji, 2019, 41(11), ～
Abstract: Because of their simple preparation process, excellent electronic conductivity and rich redox properties, transition metal sulfides are considered as the promising electrocatalyst candidates in electrocatalytic reactions. Hybrid materials in-situ grown on conductive support is a well-known strategy to enhance their electrocatalytic performance. A simple and controllable electrodeposition method was used to synthesize Co9S8-CuS nanosheet arrays in-situ grown on porous copper foam by using copper nitrate and cobalt nitrate as the metal sources. In a three-electrode system, Co9S8-CuS was used as the anode to drive electrocatalytic oxygen evolution reaction in 1M KOH and remarkable electrocatalytic performance was obtained. The overpotential to reach the current density of 50 mA/cm2 was as low as 370 mV, the corresponding to a low Tafel slope of 108 mV/dec. The remarkable electrocatalytic performance could be concluded to its available catalytic active sites and the synergistic effect on the interface of Co9S8 and CuS.
Key words: electrocatalysis; oxygen evolution reaction; electrodeposition; Co9S8-CuS; synergistic effect
引用本文:郭芬岈，马雨涵，戎怡珅，等. Co9S8-CuS纳米片阵列的电沉积制备及其电催化产氧性能研究. 化学试剂, 2019, 41(11): 1110-1114.
UIO-67材料的制备及其在水溶液中吸附亚甲基蓝染料
沈燕琼1，高永强2，杨青松2，全勇*1，李启彭*2
(1.昭通市农产品质量安全中心，云南 昭通 657000；2.昭通学院，云南 昭通 657000)
摘要：采用水热法制备UIO-67材料，使用X-射线粉末衍射仪、扫描电子显微镜和比表面积与孔隙度分析仪等手段对其进行结构表征。采用紫外可见分光光度法设计了单因素吸附实验，对UIO-67材料在水溶液中吸附亚甲基蓝染料进行研究。UIO-67材料在水溶液中吸附亚甲基蓝的最佳条件为：初始浓度为4 μg/mL，UIO-67材料用量为10 mg和溶液pH值为7.03。通过动力学模型和热力学模型分析整个吸附过程，结果表明UIO-67材料在水溶液中吸附亚甲基蓝的过程符合二级动力学模型和Freundlich模型。
关键词：UIO-67材料；水溶液；亚甲基蓝；吸附；动力学
中图分类号：O657.34 文献标识码：A 文章编号：0258-3283（2019）--
Preparation of UIO-67 materials and its adsorption for methylene blue in aqueous solution SHEN Yan-Qiong1, GAO Yong-Qiang2, YANG Qing-Song2, QUAN Yong*1, LI Qi-peng *2 (1. Agricultural Product Quality and Safety Center of Zhaotong, Zhaotong 657000, China; 2. Zhaotong University, Zhaotong, 657000, China), Huaxue Shiji, 2019, 41(11), ～
Abstract: UIO-67 Materials were prepared by hydrothermal method and characterized by X-ray powder diffraction, scanning electron microscope and specific surface area and porosity analyzer. The adsorption of methylene blue in aqueous solution by UIO-67 materials was investigated by UV-Vis method. The best adsorption conditions of UIO-67 materials for methylene blue in aqueous solution were obtained as follows: the initial concentration of methylene blue was 4 μg/mL, the content of UIO-67 materials was 10 mg and the pH value of solution was 7.03. The adsorption process of methylene blue in aqueous solution was analyzed by kinetic model and thermodynamic model. The results showed that the adsorption process of methylene blue in aqueous solution by UIO-67 materials was in accordance with the second-order kinetic model and Freundlich model.
Key words: UIO-67materials; aqueous solution; methylene blue; adsorption; dynamics
引用本文:沈燕琼，高永强，杨青松，等. UIO-67材料的制备及其在水溶液中吸附亚甲基蓝染料. 化学试剂, 2019, 41(11): 1115-1118.
纯棉织物石墨烯染色工艺探讨及性能研究
周杰1a，高普1b，马辉1a, 2，罗秋兰*1b
（1. 嘉兴学院 a.材料与纺织工程学院，b. 南湖学院, 浙江 嘉兴 314001；2. 华纺股份有限公司，山东 滨州 256617）
摘要：近些年来，柔性可穿戴的智能纺织品受到了国内外学者的广泛关注。作为智能纺织品的核心材料—导电织物，是目前的研究热点。通过一种简单、有效的方法，采用氧化石墨烯分散液对棉织物进行染色，然后用水合肼还原，得到了导电性能优异的纯棉织物，实现了染色-功能一浴化整理。通过分析不同染色浓度、pH值、染色时间对纯棉织物染色K/S值（表示织物的染色深度，K表示被测物体的吸收系数，S表示被测物体的散射系数）的影响，得出最佳的染色工艺为染色浓度10%、染色时间90 min、pH 10。此外，对最佳工艺下染色后纯棉织物的耐水洗、耐摩擦以及耐弯折电学性能和抗紫外线性能进行了表征，结果表明，织物在水洗50次、摩擦1000次、弯折1000次后，仍具有优异的耐水洗-电学稳定性、耐摩擦-电学稳定性与耐弯折-电学稳定性；石墨烯染色的纯棉织物具有非常优异的抗紫外性能，紫外线防护系数UPF值高达143.23，远远超过ASTM D6603-2012标准。
关键词：石墨烯；纯棉织物；染色效果；导电性能；抗紫外线性能
中图分类号：TS193.1 文献标识码：A 文章编号：0258-3283（2019）--
Study On the Process of Cotton Fabric and Dyeing Properties by Graphene Zhou Jie1a, Gao Pu1b, Ma Hui1a, 2, Luo Qiu-lan*1b (1a. College of Material and Textile Engineering; 1b. Nanhu college, Jiaxing University, Jiaxing 314001, China; 2. Huafang Co., Ltd, Binzhou 256617, China), Huaxue Shiji, 2019, 41(11), ～
Abstract：In recent years, flexible wearable smart textiles have attracted wide attention from scholars at home and abroad. As the core material of smart textiles, conductive fabrics are the research hotspots at present. A simple and effective method was used to dye onto cotton fabrics with graphene oxide dispersion solution and then reduced with hydrazine hydrate, which obtaineddyed cotton fabrics withexcellent electrical conductivity, finally realized dyeing-functional one-bath finishing.The effects of dyeing concentration, pH value and dyeing time on K/S value of cotton fabric were studied and analysed, the results showed that the optimum dyeing process was as dyeing concentration 10%, dyeing time 90 min and pH 10. Moreover, the washing-, friction-, bending- electrical stability, and ultraviolet resistance of dyed cotton fabrics under the optimum process were characterized. After washing for 50 times, rubbing for 1000 times, bending for 1000 times, the fabrics still have excellent washing-electrical stability, friction-electrical stability and bending-electrical stability, respectively. In addition, the graphene-based cotton fabric had excellent ultraviolet resistance, the UPF value of dyed cotton fabric was143.23, much higher than that of raw cotton fabric specimen (UPF was 19.04), which increased by 7.5 times. The ultraviolet transmittance percentage of UVA and UVB were 0.88% and 0.66%, respectively, which have decreased rapidly compared with the raw cotton fabric specimen (8.46% and 4.25%), far exceeding the excellent protection UPF grade in the American standard ASTM D6603-2012 (40+).
Key words：graphene; pure cotton fabric; dyeing effect; electrical conductivity; ultraviolet resistance
引用本文:周杰，高普，马辉，等. 纯棉织物石墨烯染色工艺探讨及性能研究用. 化学试剂, 2019, 41(11): 1119-1123.
HPLC法同时测定伤痛克酊中3种姜黄素的含量
覃彪*a, b，邓明启a，黎敏a，林锦良a,b，唐承性a
（遵义师范学院 a.化学化工学院，b.黔北特色资源应用研究实验室，贵州 遵义 563006）
摘要：建立HPLC法同时测定苗药伤痛克酊中姜黄素、去甲氧基姜黄素和双去甲氧基姜黄素的含有量。以伤痛克酊为酊剂，分析采用Shimadzu Inertsustain C18色谱柱（4.6 mm×250 mm×5 μm）；以9.6%冰醋酸水溶液-乙腈为流动相，梯度洗脱；检测波长为254 nm，流速为1.0 mL/min，柱温为30 ℃。3种姜黄素分别在各自范围内线性关系良好（r≥0.999 95），平均加样回收率分别为99.07%、100.26%、101.27%，RSD分别为0.32%、0.13%、0.11%。方法简便快捷，可用于伤痛克酊的质量控制。
关键词：HPLC法；伤痛克酊；姜黄素；去甲氧基姜黄素；双去甲氧基姜黄素
Simultaneous determination of three curcumins in Shangtongkeding by HPLC QIN Biao*1,2, DENG Ming-qi1, LI Min1, LIN Jin-Liang1, 2, TANG Cheng-Xing1 (a. College of Chemistry and Chemical Engineering; b. Key Laboratory of Utilization Research on Characteristic Resources in Qianbei, Zunyi 563002，China) Huaxue Shiji, 2019, 41(11), ～
Abstract: To establish an HPLC method for simultaneous determination of three curcumins in Shangtongkeding. Shangtongkeding is methanol tincture and the analysis of this drug was performed on the 30 ℃ thermostatic Shimadzu Inertsustain C18 column ( 4.6 mm ×250 mm，5 μm), with the mobile phase comprising of acetonitrile-water ( containing 9. 6% Glacial acetic acid) flowing at 1. 0 mL /min in a gradient elution manner，and the detection wavelength was set at 254 nm. Bisdethoxy curcumin, demethoxycurcumin and curcumin showed good linear relationships within the ranges, whose average recoveries were 99.07%、100.26%、101.27% with the RSDs of 0.11%、0.13%、0.32%, respectively. The precise and accurate method can be used for the quality control of Shangtongkeding．
Key words: HPLC method; Shangtongkeding; curcumin; bisdethoxy curcumin, dimethoxy curcumin
引用本文:覃彪，邓明启，黎敏，等. HPLC法同时测定伤痛克酊中3种姜黄素的含量. 化学试剂, 2019, 41(11): 1124-1127.
pH-敏感荧光纳米复合物的合成及其可控释放药物的性能研究
祁秀秀*1,2，李娜君2，路建美*2
（1.常州工程职业技术学院 化工与制药工程技术系，江苏 常州 213164；2.苏州大学 材料与化学化工学部，江苏 苏州 215123）
摘要：设计并合成了含肉桂醛缩醛结构疏水性基团、荧光基团罗丹明的多功能两亲性聚合物。利用其中的疏水部分与表面修饰了疏水性十八烷基三甲氧基硅烷的中空介孔二氧化硅进行自组装，得到核-壳型pH-敏感荧光纳米复合物。该纳米复合物体系具有较高的载药能力，而且能达到pH-响应释放药物的目的，同时可利用罗丹明基团进行细胞荧光成像。在体外细胞实验中，该药物载体能抑制人黑素瘤细胞A375的生长，而对人正常成纤细胞GM的生长基本不产生影响。
关键词：两亲性聚合物；纳米药物载体；pH-敏感；纳米复合物；控制释放
中图分类号：G633.8 文献标识码：A 文章编号：0258-3283（2019）--
pH-sensitive fluorescentnanocomposites for controlled drug release QI Xiu-xiu*1,2, LI Na-jun2, LU Jian-mei*2 (1. Department of Chemical and Pharmaceutical engineering, Changzhou Vocational Institute of Engineering, Changzhou, Jiangsu 2131641, China; College of Chemistry, Chemical Engineering and Materials, Soochow University, Suzhou, 215123, China) Huaxue Shiji, 2019, 41(11), ～
Abstract: The multi - functional amphiphilic polymer was designed and synthesized, which was composed of lipophilic monomer containing cinnamaldehyde acetal structure, copolymerized with hydrophilic monomer and fluorescent monomer, and then encapsulated on the surface of hollow mesoporous silica via simple self-assembly to obtain nuclear-shell multi-functional nanocomposites. The cavity can be loaded with anti-cancer drugs doxorubicin. The system not only has a higher drug loading rate, but also achieves controlled drug release, while the polymer modified rhodamine can also be used for cell angiography. In vitro, the nanocomposite selectively inhibits human melanoma cells A375 relative to human normal fibroblast GM.
Key words: amphiphilic polymer, nanocarrier, pH-sensitive, nanocomposite, controlled release
引用本文: 祁秀秀，李娜君，路建美. pH-敏感荧光纳米复合物的合成及其可控释放药物的性能研究. 化学试剂, 2019, 41(11): 1128-1132.
4-（5’-氟尿嘧啶甲基）-3-硝基苯甲酸的合成及光控性能
万永兴a，朱金丽b，孙同明b，王淼b，汤艳峰b，黄洋a，朱国华*b
（南通大学 a. 纺织服装学院，b. 化学化工学院，江苏 南通 226019）
摘要：以3-硝基-4-甲基苯甲酸为原料，经酯化、溴化，再与2, 4-双-三甲基硅烷氧基-5-氟尿嘧啶反应，最后水解合成了标题化合物，有关中间体及最终产物经NMR、FT-IR和HRMS进行结构表征。通过UV-vis、HPLC以及1HNMR跟踪监测标题化合物光照分解的过程，研究其光照分解的速率、半衰期、量子产率以及光照对5-氟尿嘧啶（5-FU）的控释效果。结果表明，标题化合物在365 nm紫外光照射下迅速分解并释放出5-FU，分解速度先快后慢，量子产率为0.028；在以水为主体的溶剂中分解速度最快；光照下5-FU持续释放，避光下停止释放，最终约有86%的5-FU被释放。
关键词：光扳机；5-氟尿嘧啶；光控释放；量子产率
中图分类号：O625.5 文献标识码：A 文章编号：0258-3283（2019）--
Synthesis and Photo-control Properties of 4-(5’-Fluorouracil-methyl)-3-nitrobenzoic Acid WAN Yong-xinga, ZHU Jin-lib, SUN Tong-mingb, WAN Miaob, TANG Yan-fengb, HUANG Yanga, ZHU Guo-hua*b（a.School of Textiles and Clothing, b.School of Chemistry and Chemical Engineering, Nantong University, Nantong 226600, China）, Huaxue Shiji, 2019, 41（11）
Abstract: The 4-(5’-fluorouracil-methyl)-3-nitrobenzoic acid photo trigger was synthesized from 3-nitro-4-methylbenzoic acid by esterification, bromination, reacting with 2, 4-bis-trimethylsiloxy-5-fluorouracil and hydrolysis. The structures were confirmed by 1HNMR, FT-IR and HRMS. The photodegradation process of the target molecular was monitored by UV-vis, HPLC and 1HNMR. The rate of photodegradation, half-life, quantum yield and the effect of illumination on 5-fluorouracil (5-FU) were well investigated. The results showed that the compound rapidly decomposed and released 5-FU under 365 nm ultraviolet light irradiation. The decomposition rate was fast followed by slow. The half-life was 3.25 min, and the quantum yield was 0.028, respectively. The decomposition rate was the highest in water-based solvent. 5-FU sustained release under UV and stopped releasing in the dark. Finally, about 86% of 5-FU was released.
Key words: photo trigger; 5-fluorouracil; light-controlled release; quantum yield
引用本文: 万永兴，朱金丽，孙同明，等. 4-（5’-氟尿嘧啶甲基）-3-硝基苯甲酸的合成及光控性能. 化学试剂, 2019, 41(11): 1133-1138.
纳米碳/纳米金葡萄糖生物传感器的制备及其影响机制
梁宇a，许朗晴a，杨迎军a，朱洪*a, b，贾明宏b
（北京农学院 a.生物科学与工程学院 农业部都市农业（北方）重点实验室，b.食品科学与工程学院 农产品有害微生物及农残安全检测与控制北京市重点实验室，北京 102206）
摘要：研究碳基纳米材料与纳米金（GNPs）颗粒的组合方式对葡萄糖（GLU）催化检测性能的影响。以离子液体（IL）作为导电性质的粘合剂，将碳基材料粘合在电极表面，并电沉积纳米金颗粒，制备成修饰电极。通过改变碳基种类（多壁碳纳米管（MWCNTs）、单壁碳纳米管（SWCNTs）、单壁碳纳米角（SWCNHs）、羧化石墨烯（C-GR））制备多种纳米碳修饰电极，对葡萄糖进行电化学检测和优化。实验发现，碳基材料性质影响葡萄糖传感器的灵敏度。其催化效果是MWCNTs>SWCNTs>C-GR>SWCNHs，该结果显示纳米材料电子加速通道对其催化性起关键作用；碳基修饰层上电沉积的单层纳米金对葡萄糖的检测灵敏。通过SEM表征发现相比于裸玻碳电极（GCE），纳米碳管上电沉积的纳米金颗粒尺寸更微小，且分散在碳纳米管上。这种组合有利于碳基与纳米金颗粒催化效应的发挥。制备了一种高灵敏无酶葡萄糖传感器，并尝试用于实际血清加标回收检测。
关键词：多壁碳纳米管；单壁碳纳米管；离子液体；金纳米粒子；葡萄糖
中图分类号：0657.1 文献标识码：A 文章编号:0258-3283（2019）
Preparation and Influencing Mechanism of Nanocarbon/Gold Nanoparticles Biosensor for Glucose LIANG Yua, XU Lang-qinga, YANG Ying-juna, ZHU Hong*a, b, JIA Ming-hongb (a. College of Biological Science and Engineering, Key Laboratory of Urban Agriculture (North China), Ministry of Agriculture, b. Key Laboratory of Detection and Control of Spoilage Microorganisms and Pesticide Residues in Agricultural Products, Beijing University of Agriculture, Beijing 102206, China), Huaxue Shiji, 2019, 41(11), ～
Abstract: It investigated the combination of carbon-based nanomaterials and gold nanoparticles (GNPs) on the catalytic performance of glucose (GLU). Ionic liquid (BmimBF4, IL) was used as a binder for conductive properties. Carbon-based material was modified on glass carbon electrode (GCE), then GNPs were electrodeposited on it. Different carbon-based species [multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs), single-walled carbon nanohorns (SWCNHs), Carboxylated graphene (C-GR)], were used to prepare modified electrodes. Experiments showed the property of carbon-based materials affected the sensitivity of glucose sensors. The catalytic effect was MWCNTs>SWCNTs>C-GR>SWCNHs. The results showed that electron acceleration channel of the nano-material plays a key role in the catalytic activity. The single-layer GNPs, electrodeposited on the carbon-based modification layer, was sensitive to glucose detection. By SEM characterization. It was found that the GNPs deposited on the carbon nanotubes got a smaller size than GNPs deposited on GCE. The combination of carbon-based material and GNPs facilitated the catalytic effect. A sensitive enzyme-free glucose sensor was prepared and applied to actual serum spike recovery detection.
Key words: multi-walled carbon nanotubes; single-walled carbon nanotubes; ionic liquid; gold nanoparticles; glucose
引用本文: 梁宇，许朗晴，杨迎军，等. 纳米碳/纳米金葡萄糖生物传感器的制备及其影响机制. 化学试剂, 2019, 41(11): 1139-1144.
浓缩型玻璃清洗剂的研制及其性能研究
陶源，张威*，王丰收
（上海发凯化工有限公司，上海 201505）
摘要：研发了一种浓缩型防雾玻璃清洗剂。选用生物降解性较好的表面活性剂为主表面活性剂，且通过正交试验确定了其最优配方组合：FMEE的添加质量分数为6%，APG0810的添加质量分数为4%，异构十三醇聚氧乙烯醚的添加质量分数为3%，AES的添加质量分数为2%，AEC9Na、聚醚改性聚硅氧烷、乙二醇丁醚、缓蚀剂和消泡剂的添加质量分数分别为0.2%、0.5%、5%、0.5%、0.3%。对防雾成分进行筛选，对清洗工艺条件进行了考察，且在此基础上进行了重复清洗实验。研究结果表明：当清洗剂稀释12.5倍，温度为40 ℃、清洗时间为7 min 时，清洗剂的清洗效果最好，污垢去除率为99.2%；重复清洗5次后，对污垢仍有较好的清洗效果，去除率高达90.0%；选择聚醚改性聚硅氧烷作为防雾成分具有很好的防雾效果。
关键词：玻璃清洗剂；防雾；表面活性剂；浓缩
中图分类号：TQ649 文献标识码：A 文章编号：0258-3283（2019）--
Preparation and Properties of a Concentrated Glass Cleaning Agent TAO Yuan, ZHANG Wei (Shanghai Fine Chemical Co., Ltd, Shanghai 201505, China), Huaxue Shiji, 2019, 41(11), ～
Abstract：A concentrated antifogging glass cleaning agents were investigated and developed, eco-friendly and biodegradable surfactants were selected as main surfantants. The optimal combination of formula has been obtained as follows: FMEE 6.0 wt%, APG0810 4.0 wt%,iso-C13AEO 3.0 wt%, AES 2.0 wt%, AEC 9Na, AEC9Na, polyether modified polysiloxane, ethylene glycol monobutyl ether, corrosion inhibitor, antifoam agent are 0.2% wt、0.5% wt、5% wt、0.5% wt、0.3% wt respectively. And antifogging additives has been investigated and the cleaning process has been optimized and repeated cleaning experiments have been carried out on this basis. The results show that the cleaning efficiency proves to be the highest when the glass specimens dilute 12.5 times are supersonically rinsed for 7 min at 40 ℃, with its removal rate being 99.2 %. After 5 times of repeated cleaning, the removal rate is as high as 90.0%, and it has good antifogging effect selected polyether modified polysiloxane as film-forming agent.
Keywords：glass cleaning agent; antifogging; surfactant；concentrated
引用本文: 陶源，张威，王丰收. 浓缩型玻璃清洗剂的研制及其性能研究. 化学试剂, 2019, 41(11): 1145-1149.
1，3-偶极子参与不对称构建氧化吲哚C（3）位五元螺环化合物的研究进展
陈凯镔，朱宝磊，钟伟鹏，陈清，林宁*
（广西中医药大学 药学院，广西壮瑶药工程技术研究中心，广西 南宁 530001）
摘要：螺环氧化吲哚化合物广泛存在于天然产物中，具有抗肿瘤、抗菌、抗微生物和抗炎等诸多生物活性，常作为先导化合物用于新药发现。因其结构复杂，具有多个立体中心，合成过程中立体选择性难以控制，因此含该类骨架化合物的不对称合成是研究者的关注热点。以 1，3-偶极子为底物，通过不对称[3＋2]环加成反应是构建手性五元螺环氧化吲哚化合物的重要方法。按 1，3-偶极子进行分类，对近年来该类化合物的不对称构建方法进行综述，为该类化合物的合成提供参考。
关键词：螺环氧化吲哚；1，3-偶极子；不对称催化；研究进展
中图分类号：0621.3 文献标识码：A 文章编号：0258-3283（2019）--
Progress for Construction of Chiral Five-membered Spirooxindoles by 1, 3-Dipoles Based on C (3) Indole CHEN Kai-Bin, ZHU Bao-Lei, ZHONG Wei-Peng, CHEN Qing, LIN Ning* (Guangxi Zhuang Yao Medicine Center of Engineering and Technology, School of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001, China) Huaxue Shiji, 2019, 41(11), ～
Abstract：The compounds of spirooxindole are widely found in many natural products. They are often used as lead compounds in new drug discovery by the reason of the bioactivities of anti-tumor, anti-bacterial, anti-microbial, and anti-inflammatory. Due to its complex structures, multiple stereocenters and stereoselectivity, the asymmetric synthesis of such skeleton compounds have captured tremendous attention from the researchers. Asymmetric [3+2] cycloaddition with 1, 3-dipoles is an important method for the construction of chiral five-membered spirooxindoles. The progress of synthesis of chiral five–membered spirooxindoles by 1, 3-dipoles in recent years was reviewed, which provide valuable information for the synthesis of these compounds.
Key words: spirooxindoles; 1, 3-dipole; asymmetric catalysis; research progress
引用本文: 陈凯镔，朱宝磊，钟伟鹏，等. 1，3-偶极子参与不对称构建氧化吲哚C（3）位五元螺环化合物的研究进展. 化学试剂, 2019, 41(11): 1150-1161.
QuEChERS-UPLC-MS/MS法检测腐败人血中的雷/公藤生物碱
钟世豪a，任昕昕*b，于哲a，于忠山b，杨孟京a
（中国人民公安大学 a. ，b. 公安部物证鉴定中心，北京 100038）
摘要：建立了快速检测腐败血中雷公藤春碱、雷公藤吉碱、雷公藤定碱、雷公藤次碱的QuEChERS结合超高效液相色谱-三重四级杆质谱(UPLC-MS/MS)检测方法。方法前处理采用乙腈作为提取剂，60 mg NaCl和70 mg无水MgSO4作为盐析剂，并利用30 mg N-丙基乙二胺（PSA）、10 mg石墨化碳黑（GCB）与50 mg无水MgSO4为净化剂，UPLC-MS/MS采用多反应监测模式。方法中4种生物碱的检测限为0.02～0.06 μg/L，定量限为0.10～0.20 μg/L，在3种加标水平下平均回收率为88.1%～112.9%，精密度在1.1%～5.7%之间，基质效应相对沉淀蛋白法改善4.77%～39.70%。方法操作简单、灵敏度高，适用于腐败血中雷公藤生物碱的快速检测。
关键词：QuEChERS前处理方法；液相色谱串联质谱；雷公藤生物碱；腐败人全血
中图分类号：O615.4 文献标识码：A 文章编号：0258-3283（2019）11--
Detection of Tripterygium Alkaloids in Putrefied Blood by QuEChERS-Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry ZHONG Shi-haoa, REN Xin-xin*b, YU Zhea, YU Zhong-shanb, YANG Meng-jinga (a. , b. Institute of Forensic Science, Ministry of Public Security, People's Public Security University of China, Beijing 100038, China),Huaxue Shiji, 2019, 41(11), ～
Abstract: A QuEChERS-Ultra High Performance Liquid Chromatography-triple quadrupole Mass Spectrometry (UPLC-MS/MS) method was developed for the rapid detection of four tripterygium alkaloids (Wilfortrine, Wtlforgine ,Wtlfordine and Wilforine) in the putrefied blood. The method used acetonitrile as extractant, 60 mg of NaCl and 70 mg of MgSO4 as salting-out agent. 30 mg of PSA，10 mg of GCB and 50 mg of MgSO4 as purifying agent. In UPLC-MS/MS detection, multi-reaction monitoring mode, qualitative ion pair and standard curve method was used. The LOD of four tripterygium alkaloids was 0.02～0.06μg/L, and the LOQ was 0.10～0.20 μg/L. The average recovery was 88.1～112.9% at the three added levels, and the intra-day and inter-day precision was between 1.1% and 5.7%. Compared with protein precipitation, the Matrix effect was improved 4.77%～39.70%.The method is simple in operation, high in sensitivity and wide in linear range. It is suitable for the accurate and rapid detection of tripterygium alkaloids in putrefied blood.
Key words：QuEChERS; HPLC-MS/MS; tripterygium alkaloid; putrefied blood
引用本文: 钟世豪，任昕昕，于哲，等. QuEChERS-UPLC-MS/MS法检测腐败人血中的雷/公藤生物碱. 化学试剂, 2019, 41(11): 1162-1167.
电喷雾萃取电离质谱监测Doebner-Von Miller反应
朱潇，杨小丽，刘一帅，谢宗波*，乐长高*
（东华理工大学 应用化学系，江西省质谱科学与仪器2011协同创新中心，江西 南昌 330013）
摘要：分别以碘和对甲苯磺酸为催化剂，用电喷雾萃取电离质谱（EESI-MS）在线监测了正丁醛与苯胺、对甲苯胺、对甲氧基苯胺等3种芳香胺间的Doebner-Von Miller反应。通过捕捉到的产物、中间体及反应物的准分子离子信号，推测了反应机理。苯胺首先与醛进行亲核加成消除反应生成亚胺；亚胺再与另一分子醛进行迈克尔加成反应；最后经自身环化-缩合脱水-脱氢芳构化，得喹啉类化合物。比较碘和对甲苯磺酸的催化效果时发现，以对甲苯磺酸为催化剂时反应达到平衡所需时间较短。
关键词：Doebner-Von Miller反应；反应机理；监测；电喷雾萃取电离质谱
中图分类号：O626.32 文献标识码：A 文章编号：0258-3283（2019）--
Monitoring the catalytic process of Doebner-Von Miller Reaction by EESI-MS ZHU Xiao, YANG Xiao-li, LIU Yi-shuai, XIE Zong-bo*, LE Zhang-gao* (Jiangxi 2011 Joint Center for the Innovative Mass Spectrometry and Instrumentation, Department of Applied Chemistry, East China University of Technology, Nanchang 330013, China) Huaxue Shiji, 2019, 41(11), ～
Abstract: The iodine or p-toluenesulfonic acid catalyzed reaction between three aromatic amines and n-butyraldehyde was monitored online by EESI-MS (extractive electrospray ionization tandem mass spectrometry), and the quasi molecular ion signals of reactant, intermediate and product were captured. Then the presumed mechanism was deduced: aniline and aldehyde were eliminated by addition reaction to form an imine, and the intermediate was formed from imine and another aldehyde by Michael addition reaction, and then the quinoline derivative was produced by the intermediate’s self-cyclization dehydration and dehydrogenation aromatization. Comparing the catalytic effects of iodine and p-toluene sulfonic acid, it was found that the reaction time was shorter when p-toluene sulfonic acid was used as catalyst.
Key words:Doebner-Von Miller reaction; reaction mechanism; monitoring; EESI-MS
引用本文: 朱潇，杨小丽，刘一帅，等. 电喷雾萃取电离质谱监测Doebner-Von Miller反应. 化学试剂, 2019, 41(11): 1168-1172.
超高效液相色谱-串联质谱法同时测定土壤中46种禁限用农药
刘志荣，张平，谢楠，郭朝晖，马潇，杨平荣*
(甘肃省药品检验研究院，甘肃 兰州 730070)
摘要：建立了同时测定土壤中46种禁限用农药的改进QuEChERS超高效液相色谱-串联质谱（UHPLC-MS/MS）方法。在最佳流动相组成下，46种禁限用农药灵敏度较高，结果可靠。质谱分析采用电喷雾电离，正负离子扫描、依赖保留时间的动态多反应监测模式（dMRM）下，以基质匹配内标法定量。结果表明，46种禁限用农药在各自的浓度范围内线性关系良好（R2≥0.99）；3个添加水平（10、50、100 μg/kg）下，46种禁限用农药的回收率为53%～129%，相对标准偏差（RSD，n = 6）不大于20.0%，46种禁限用农药的定量限为1～20 μg/kg。本研究为土壤中准确、高效、经济的检测禁限用农药提供了可靠依据。
关键词：土壤；禁限用农药；QuEChERS；超高效液相色谱-串联质谱
中图分类号：O65.0655 文献标识码：A 文章编号：0258-3283（2019）
Simultaneous Determination of 46 Forbidden and Restricted Pesticide Residues in Soil by Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry LIU Zhi-rong, ZHANG Ping, XIE Nan, GUO Zhao-hui, MA Xiao, YANG Ping-rong* (Gansu Provincial Institute of Drug Control, Lanzhou 730070, China), Huaxue Shiji, 2019, 41（11）
Abstract: In this work, a multiresidue method for the analysis of 46 forbidden and restricted pesticide residues in soil was developed by using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) combined with a modified QuEChERS procedure. The optimal mobile phase composition (Water containing 10 mmol/L ammonium formate and 0.1% formic acid) produced high sensitivity and reliable results. The mass spectrometer was operated in dynamic multiple reaction monitoring (dMRM) mode with positive and negative electrospray ionization. The pesticide residues were quantified by matrix matched standard solution-internal standard method. All calibration curves showed good linearity (R2>0.99) within the test ranges. The method was validated by analysis of soil samples, spiked at three levels (10, 50, 100 μg/kg). The recovery values were generally between 53% and 118% and the relative standard deviation values (%RSDs) were below 20.0%. The limits of quantification of 46 forbidden and restricted pesticides were 1 ～ 20 μg/kg. This work provided a reliable basis for accurate，efficient and economical detection of forbidden and restricted pesticides in soil．
Key words: soil; forbidden and restricted pesticides; QuEChERS; ultra high performance liquid chromatography-tandem mass spectrometric (UHPLC-MS/MS)
引用本文: 刘志荣，张平，谢楠，等. 超高效液相色谱-串联质谱法同时测定土壤中46种禁限用农药. 化学试剂, 2019, 41(11): 1173-1179.
甲醇-水流动相HPLC测定银杏萜内酯方法优化
张佳丽，杜小弟，吴琼，雷家珩*
（武汉理工大学 化学化工与生命科学学院，湖北 武汉 430070）
摘要：优化了甲醇-水流动相HPLC测定银杏萜内酯的方法，建立了线性回归方程，并与药典正丙醇-四氢呋喃-水流动相方法进行比较。在此基础上，用两种方法对银杏叶、银杏外种皮、白果以及银杏叶提取物（EGB）样品中的萜内酯含量进行了对照分析。结果表明，甲醇-水梯度洗脱基线噪音小，柱效高，分离时间短。优化的洗脱条件为：甲醇-水为流动相，0 ～ 2 min，0 ～ 20%甲醇；2 ～ 32 min，20% ～ 60%甲醇，建立的方法在50 ～ 2000 mg/L的浓度范围内具有良好的线性关系，检出限为0.05 ～ 0.09 μg，不同浓度水平的加标回收率为92.4% ～ 101.6%，RSD值为2.7% ～ 5.1%。两种方法测定银杏萜内酯没有明显差别，其中测定银杏叶中白果内酯、银杏内酯C、银杏内酯A、银杏内酯B的相对误差分别为0.86、4.2、1.7、3.9。
关键词：银杏内酯；萜内酯；高效液相色谱-蒸发光散射；仪器分析
中图分类号：R284.1 文献标志码：A 文章编号：0258-3283（2019）--
Optimization for Determination Method of Terpene Lactones with Methanol-water as Mobile Phase by HPLC ZHANG Jia-li, DU Xiao-di, WU Qiong, LEI Jia-heng* ( School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China), Huaxue Shiji, 2019, 41(11)
Abstract: Optimized HPLC method for determination of terpene lactones in Ginkgo biloba by methanol-water mobile phase. A linear regression equation was established and compared with the pharmacopoeial n-propanol-tetrahydrofuran-water mobile phase method. The content of terpene lactones in Ginkgo leaf, exotestal, seed and extract were compared by these two methods. The results showed the methanol-water gradient elution has lower baseline noise, higher column efficiency and shorter separation time compared with the pharmacopoeia method. The optimized elution conditions: methanol-water as mobile phase, 0 ～ 2 min, 0% ~ 20% methanol; 2 ～ 32 min, 20% ~ 60% methanol. The established method has a good linear relationship in the concentration range of 50 mg/L. The detection limit is 0.05 ~ 2000 mg/L, and the recoveries at different concentration levels is 92.4% ~ 101.6% with RSD 2.7% ~ 5.1%. There was no significant difference in the determination of terpene lactones between these two methods. The relative errors of bibobalide, ginkgolide C, ginkgolide A, and ginkgolide B in Ginkgo leaf were 0.86, 4.2, 1.7, 3.9.
Key words: ginkgolides; terpene lactones; HPLC-ELSD; instrumental analysis
引用本文: 张佳丽，杜小弟，吴琼，等. 甲醇-水流动相HPLC测定银杏萜内酯方法优化. 化学试剂, 2019, 41(11): 1180-1183.
一种磷钨杂多酸冠醚型超分子晶体材料的制备及性能研究
朱春立，刘洋*，王晨丽，秦刘磊，郑晓媛，刘尊奇*
（新疆农业大学 化学工程学院，新疆 乌鲁木齐830052）
摘要：采用H管扩散法合成一种Keggin型磷钨杂多酸冠醚超分子功能型晶体材料(C6H5-NH2.5+0.5)6(18-crwon-6)3[PW12O40]3-(1)(简称化合物C6C3P)，并通过红外光谱(IR)、元素分析和单晶X-射线衍射对其进行了结构表征。低温（100 K）测试结果表明，该化合物属于六方晶系，空间群为R-3，晶体参数为a＝25.3720(9) Å、b＝25.372 Å、c＝14.3738(5) Å、α＝90.00°、β＝90.00°、γ＝120.00°、V＝8013.3 Å3、Z＝3、Rint＝0.0554。化合物C6C3P包括一分子质子化苯胺分子、1/6[PW12O40]3-阴离子和半分子冠醚，其中两个苯胺分子与冠醚通过氢键相互作用形成三聚体结构。变温-介电常数测试显示，在230K附近出现明显介电异常。
关键词：杂多酸；18-冠醚-6；氢键；超分子
中图分类号：O623 文献标识码：A 文章编码：0258-3283（2019）--
Preparation and Properties of Supramolecular Crystalline Material with Phosphotungstic
HeteropolyAcidand Crown Ether ZHU Chun-li, LIU Yang*, WANG Chen-li, QIN Liu-lei, ZHENG Xiao-yuan, LIU Zun-qi* (Chemical Engineering College, Xinjiang Agricultural University, Urumqi 830052, China), Huaxue Shiji, 2019, 41(11), ～
Abstract：A Keggin supramolecular functional crystalline material of phosphotungsticheteropolyacid and crown ether was prepared by H-tube diffusion method and characterized via infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. Test results at low temperature(100 K) showed that the compound belongs to hexagonal crystal system, space groupR-3, a=25.3720（9）Å, b=25.372 Å, c=14.3738（5）Å, α=90.00°, β=90.00°, γ=120.00°, V=8013.3 Å3,Z=3, Rint=0.0554. X-ray diffraction analysis revealed that the molecular structure of C6C3P consists of one protonated aniline molecule, one-sixth [PW12O40]3- anion, one half crown ether molecule. Among them, two aniline molecules interacted with crown ethers via hydrogen bonds to form the trimer structures. Temperature-dependence dielectric measurement showed obvious dielectric anomaly at ca. 230 K.
Key words：heteropolyacid; 18-crown -6; hydrogen bond; supramolecular
引用本文: 朱春立，刘洋，王晨丽，等. 一种磷钨杂多酸冠醚型超分子晶体材料的制备及性能研究. 化学试剂, 2019, 41(11): 1184-1188.
联吡啶取代基二(4-氨基-1,2,4-三氮唑-3-硫醚)的合成及表征
易君明，郑玉国，陈明华*
（兴义民族师范学院 生物与化学学院，化学合成及环境污染控制和生态修复技术实验室，贵州 兴义 562409）
摘要：以2,2’-联吡啶-3,3’-二甲酰肼为原料，经过成环反应制备中间体2,2’-联吡啶-3,3’-二[5-(4-氨基-1,2,4-三氮唑-3-硫酮))]，再经过醚化反应得到5个2,2'-联吡啶-3,3'-二(4-氨基-1,2,4-三氮唑-3-硫醚)系列目标化合物，其结构通过1HNMR、13CNMR、MS、IR、元素分析以及单晶X-射线衍射等技术进行表征。结果表明，中间体及目标化合物均存在转阻异构体，硫醚化合物的分子结构形状受末端基团影响较大，中间体可与对称四甲基六元瓜环形成1 : 2的主-客体超分子配合物。
关键词：2,2'-联吡啶-3,3'-二甲酰肼；2,2'-联吡啶-3,3'-二(4-氨基-1,2,4-三氮唑-3-硫醇)；硫醚；对称四甲基六元瓜环；晶体结构；超分子
中图分类号：O626.2 文献标识码：A 文章编号：0258-3283（2019）--
Synthesis and Characterization of 2,2'-Bipyridine Substitued 4-Amino-1,2,4-triazole Thioethers YI Jun-ming, ZHENG Yu-guo, CHEN Ming-hua* (Key Laboratory of Chemical Synthesis and Environmental Pollution Control-remediation Technology, School of Biology and Chemistry, Xingyi Normal University for Nationalities, Xingyi 562409) Huaxue Shiji, 2019, 41(11), ～
Abstract: A series of novel 2,2'-bipyridine-3,3'-bis(4-amino-1,2,4-triazole-3-thioether) and the intermediate of 2,2'- bipyridine-3,3'-bis(4-amino-1,2,4-triazole-3-thiol) were synthesized from the starting reagent of 2,2'-bipyridine- 3,3'-diformylhydrazine. The structures of these compounds were conformed by 1H NMR,13C NMR, IR, elemental analysis, and single-crystal X-ray diffraction analysis. The result of single-crystal X-ray diffraction revealed that both the intermediate and target compounds have chiral atropisomerics. The total molecular shape of thiother is greatly affected by their terminal groups. Two intermediates were outersided the two ports of TMeQ[6] then self-assembly formed 1 : 2 host-guest complex in aqueous solution of dilute hydrochloric acid.
Key words：2,2'-bipyridine-3,3'-diformylhydrazine; 2,2'-bipyridine-3,3'-bis(4-amino-1,2,4-triazole-3-thiol)；thioether; tetramethyl substituted cucurbit[6]uril; crystal structure; super molecule
引用本文: 易君明，郑玉国，陈明华. 联吡啶取代基二(4-氨基-1,2,4-三氮唑-3-硫醚)的合成及表征. 化学试剂, 2019, 41(11): 1189-1196.
艾代拉里斯中间体(S)-2-(1-氨基丙基)-5-氟-3-苯基-4(3H)-喹唑啉酮三氟乙酸盐的合成及晶体结构表征
张旭光，刘春芬*，慕金超
(徐州工业职业技术学院，江苏 徐州 221140)
摘要：以2-氨基-6-氟苯甲酸和L-2-(叔丁氧羰基氨基)丁酸为起始原料，经环合，再与苯胺反应，然后在三氟乙酸的作用下，脱Boc、成三氟乙酸盐，即得(S)-2-(1-氨基丙基)-5-氟-3-苯基-4(3H)-喹唑啉酮三氟乙酸盐化合物。所合成的产物通过红外光谱、核磁共振氢谱进行了表征，并通过自然挥发法得到了该品的单晶，经X-单晶衍射分析表征了其结构。
关键词：艾代拉里斯中间体；(S)-2-(1-氨基丙基)-5-氟-3-苯基-4(3H)-喹唑啉酮三氟乙酸盐；合成；晶体结构
中图分类号：O782 文献标识码：A 文章编号：0258-3283(2019)--
Synthesis and Crystal Structure of Idelalisib Intermediate (S)-2-(1-amino-propyl)-5-fluoro-3- phenyl-3H-quinazolin-4-one Trifluoroacetate ZHANG Xu-guang, LIU Chun-fen*, MU Jin-chao (Xuzhou college of industrial technology, Xuzhou, 221140, China), Huaxue Shiji, 2019, 41(11), ～
Abstract: The title compound was synthesized by 2-amino-6-fluoro-benzonic acid and (2S)-2-[(tert-butoxycarbonyl)amino]butanoic acid as start material obtaining (S)-tert-butyl (1-(5-fluoro-4-oxo-4H-benzo[d][1,3]oxazin-2-yl)propyl)carbamate by cyclization reaction, then reacted with aniline to obtain (S)-tert-butyl (1-(5-fluoro-4-oxo-3-phenyl-3,4- dihydroquinazolin-2-yl)propyl)carbamate. And the title compound was prepared by the reaction with trifluoroacetic acid. Compound 1 was confirmed by IR, 1HNMR, and single crystal X-ray crystallography.
Key words: idelalisib intermediate; (S)-2-(1-amino-propyl)-5-fluoro-3-phenyl-3H-quinazolin-4- one trifluoroacetate; synthesis; crystal structure
引用本文: 张旭光，刘春芬，慕金超. 艾代拉里斯中间体(S)-2-(1-氨基丙基)-5-氟-3-苯基-4(3H)-喹唑啉酮三氟乙酸盐的合成及晶体结构表征. 化学试剂, 2019, 41(11): 1197-1200.
葡萄糖和丙氨酸的美拉德反应及其在烟草中的应用研究
苏加坤1，赵琪2，李瑞丽 1, 2，徐达1，张峻松2，蔡继宝*1
（1. 江西中烟工业有限责任公司 江西 南昌 330096；2.郑州轻工业大学 食品与生物工程学院 郑州 450001）
摘要：为加大美拉德反应产物（MRPs）在卷烟加香中的开发和应用，以葡萄糖和丙氨酸为原料，通过单因素试验和正交试验考察了反应时间、体系初始pH、反应温度、糖氨物质的量比对MRPs的影响，并对MRPs进行GC-MS成分分析及感官评价。结果表明：最佳反应条件为：反应时间为6 h，体系初始pH值为10.0，反应温度为95 ℃，糖氨物质的量比为2:1。反应产物中挥发性香味成分主要有呋喃类成分2种、呋喃酮类3种、吡喃酮类3种。感官评价结果表明，葡萄糖和丙氨酸的MRPs加入卷烟中可以降低杂气和刺激性、增加回甜感、提高烟气轻松感，最佳添加量为0.10%。
关键词：葡萄糖；丙氨酸；美拉德反应；GC-MS；感官评价
中图分类号：TS 41 文献标志码：A 文章编号：0258-3283（2019）--
Maillard Reaction of Glucose and Alanine and Its Application in Tobacco SU Jia-kun1, ZHAO Qi2, LI Rui-li1, 2, XU Da1, ZHANG Jun-song2, CAI Ji-bao*1（1. China Tobacco Jiangxi Industrial Co, Ltd., Nanchang 330096, China; 2. Colloge of Food and Bioengineering, Zhengzhou University of light Industry, Zhengzhou 450001, China), Huaxue Shiji, 2019, 41(11), ～
Abstract: In order to increase the development and application of Maillard reaction products in cigarette flavoring, the effects of reaction time, initial pH, reaction temperature and sugar ammonia ratio on Maillard reaction products (MRPs) were investigated by single factor experiment and orthogonal test with glucose and alanine as raw materials. The GC-MS component analysis and sensory evaluation of MRPs were performed. The optimal reaction conditions were that reaction time was 6 h, the initial pH value of the system was 10.0, the reaction temperature was 95 °C, and the molar ratio of sugar to ammonia was 2:1. The volatile aroma components in the reaction product mainly include two kinds of furan components, three kinds of furanones, and three pyranones. Sensory evaluation results showed that the MRPs of glucose and alanine could significantly reduce the irritating and heterogeneous, increase the sweetness and improve the relaxation of smoke. The optimal addition amount was 0.10%.
Key words: glucose; alanine; Maillard reaction; GC-MS; sensory evaluation
引用本文: 苏加坤，赵琪，李瑞丽，等. 葡萄糖和丙氨酸的美拉德反应及其在烟草中的应用研究. 化学试剂, 2019, 41(11): 1201-1205.
黄香楝中黄酮、多酚的提取工艺
杨新周1，刘汗青2，李秀林2
（1.德宏师范高等专科学校 民族医药研究所，云南 德宏 678400；2.瑞丽海关综合技术中心，云南 德宏，678600）
摘要: 利用水浴-回流法提取黄香楝中的黄酮、多酚，并用分光光度法分析了其含量。研究了不同乙醇体积分数、液料比、提取温度、时间对样品中黄酮、多酚提取效率的影响。通过实验得出黄香楝中黄酮和多酚提取的最优工艺为：提取温度为85 ℃，料液质量浓度比为1:45，时间为4 h，乙醇体积分数为50%。在此条件下黄香楝中黄酮、多酚能够被同时提取，此操作简单、稳定性好、结果准确。黄香楝黄酮和多酚含量分别为4.85、4.79 mg/g。结果表明，水浴-回流法能够同步提取黄香楝中的黄酮、多酚类物质。
关键词: 黄香楝；黄酮；多酚；回流提取
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2019）--
Extraction Technology of Flavonoids, Polyphenols in Hesperethusa crenulata Bark YANG Xin-zhou1, LIU Han-qing2, LI Xiu-lin2 (1.The Research Institute of Ethnic Minority Medicine, Dehong Teachers’ College, Dehong 678400, China；2. Integrated Technical Center of Customs in Ruili, Dehong 678600, China), Huaxue Shiji, 2019, 41(11), ～
Abstract: by using water bath-reflux method and spectrophotometry, the contents of flavonoids and polyphenols in the Hesperethusa crenulata bark were investigated. In addition, the effects of different ethanol volume fraction, liquid ratio, extraction temperature and time on extraction efficiency of flavonoids and polyphenols were investigated. The results showed that, the best extracting technology for flavonoid ,polyphenol in Hesperethusa crenulata bark follows : extraction temperature: 85 ℃, liquid ratio: 1:45, time 4 h, ethanol volume fraction: 50%, respectively. The extracted process stability was good, the results were accurate and reliable, and the process was simple and operable. The flavonoids and total phenol content was 4.85, 4.79 mg/g, The water bath-reflux method can simultaneously extract the flavonoids, polyphenols in the Hesperethusa crenulata bark.
Key words: hesperethusa crenulata bark; flavonoids; polyphenol; reflux extraction
引用本文: 杨新周，刘汗青，李秀林. 黄香楝中黄酮、多酚的提取工艺. 化学试剂, 2019, 41(11): 1206-1209.
2-甲基-3-苯基苯甲酸的合成方法研究
王晓雅*，黄星星
（安康学院 化学化工学院，陕西 安康 725000）
摘要：标题化合物是一种具有广泛应用前景的重要化工中间体，然而，关于该化合物的合成研究很少报道。报道了两种新的合成标题化合物方法：1）以2-甲基-3-氯联苯为原料制备Grignard试剂，然后通入CO2，水解来制备；2）以2-甲基-3-苯基苯甲醇为原料用Jones 试剂选择性氧化制备该化合物。并研究了试剂的用量与反应时间及温度的关系，产率均达到90%以上。这两种新方法具有合成工艺简单、产率高、工艺绿色环保等优点。所得化合物经IR和1H NMR确认。
关键词：Grignard试剂；Jones试剂；选择性氧化；2-甲基-3-苯基苯甲酸
中图分类号：0625.5 文献标识码：A 文章编号：0258-3283（2019）
Synthesis Method of 2-Methyl-3-phenylbenzoic Acid WANG Xiao-ya*, HUANG Xing-xing (School of Chemistry and Chemical Engineering, Ankang University, Ankang 725000, China), Huaxue Shiji, 2019, 41（11）
Abstract: 2-Methyl-3-phenyl is an important chemical intermediate with broad application prospect. However, the synthesis process of this compound had been few reported. Two new methods for synthesizing of the title compound were reported in this work. A kind of synthesis is to prepare Gringnard reagents from 2-methyl-3-chlorinated biphenyls, which are then fed with CO2 and hydrolyzed .Another approach is to selectively oxidize 2-methyl-3-phenylbenzyl methanol with Jones reagent to obtain the title compound .The relationship between the amount of reagent and reaction time and temperature was investigated . The results show that these two new methods have the advantages of simple synthesis, high yield and green process. The compounds were confirmed by IR and 1H NMR.
Key words : Gringnard reagent；Jones reagent；selective oxidation；2-methyl-3-phenylbenzoic acid
引用本文:王晓雅，黄星星. 2-甲基-3-苯基苯甲酸的合成方法研究. 化学试剂, 2019, 41(11): 1210-1213.
氟草烟异辛酯的合成研究
黄生建
(浙江今晖新材料股份有限公司，浙江 上虞 312369)
摘要：标题化合物是一种含氟高效、低毒、低残留的吡啶类除草剂，广泛应用于防除阔叶类杂草。以2,3,4,5,6-五氯吡啶为原料，通过氟代、氨化、水解，再与氯乙酸甲酯缩合，最后在氯酞酸四丁酯催化下与仲辛醇发生酯交换反应来制备标题化合物。4步反应总收率77.8%，产物纯度99.5%，化合物结构经过1HNMR 和 13CNMR 确证。其中所用的溶剂和催化剂均可回收套用，减少了对环境的污染。此外，氨化和水解反应一锅法完成。工艺条件温和、操作简单、成本低，适合工业化生产。
关键词：2,3,4,5,6-五氯吡啶；氟化钾；合成
中图分类号：TQ45 文献标识码：A 文章编号：0258-3283（2019）--
Synthesis of Fluroxypr-mepthyl HUANG Sheng-jian (Zhejiang Sunfit Advanced Materials Co. Ltd., Shangyu312369, China), Huaxue Shiji, 2019, 41(11), ～
Abstract：The title compound is a fluorine-containing pyridine herbicide with high efficiency, low toxicity and low residue, which is widely used in broad-leaved weeds. 2,3,4,5,6-Pentachloropyridine was used as raw materials to prepare the title compound by fluorination, amination, hydrolysis and condensation with methyl chloroacetate followed by transesterification with sec-octanol under the catalysis of tetrabutyl titanate. The total yield of the 4-step reaction with a purity of 99.5%, and an overall yield of 77.8%, and the structure of the compound was confirmed by 1HNMR and 13CNMR. The solvent and catalyst used can be recycled, and used to reduce environmental pollution. Besides, amination and hydrolysis were completed in one pot. The process condition was mild, simple in operation, and was suitable for industrialized production.
Key words: 2,3,5,6-Tetrafluoroterephthalyl alcohol; potassium fluoride; synthesis
引用本文:黄生建. 氟草烟异辛酯的合成研究. 化学试剂, 2019, 41(11): 1214-1217.
