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《化学试剂》2019年第9期中英文摘要

白藜芦醇的合成研究进展

夏曦,徐嘉琪,胡越高,陈煜,杨鸿均*,赵志刚

(西南民族大学 化学与环境保护工程学院,四川 成都  610041

 

摘要:白藜芦醇是一种作用广泛的天然多酚类药物,是在植物遭受外界胁迫时产生的一种植物抗毒素,主要存在于葡萄等浆果类植物中,目前已在100种植物中被发现。近年来的研究表明,白藜芦醇具有多种生物活性和药理作用,尤其在抗氧化、抗肿瘤和治疗心血管疾病方面有非常显著的作用,可广泛应用于医药、食品、化妆品和保健品等领域。由于生物提取成本较高,因此白藜芦醇的合成成为国内外研究的热点。目前,白藜芦醇的合成方法主要有生物合成法和化学合成法。其中,生物合成的产量小,且操作复杂,所以化学合成方法成为了主要研究方向。化学合成白藜芦醇的方法主要有Heck反应、Wittig反应、Perkin反应、Suzuki 反应、有机金属法等,对白藜芦醇的化学合成方法进行了综述,以期为进一步开发利用白藜芦醇提供依据。

关键词:白藜芦醇;Perkin反应;Heck反应;Wittig反应;Suzuki反应;有机金属法;合成

中图分类号:O621. 3      文献标识码:A      文章编号:0258-3283201909--

 

Progress on The Synthesis of Resveratrol XIA Xi, XU Jia-Qi, HU Yue-Gao, CHEN Yu, Yang Hong-Jun*, ZHAO Zhi-Gang (College of Chemistry & Environment Protection Engineering, Southwest Minzu University, Chengdu 610041, China), Huaxue Shiji, 2019, 41(9), ~

Abstract: Resveratrol, a natural polyphenols compound that has been extensively investigated for diverse range of biological activities, is a phytoalexin compound that produced by plants under external stress. It has been found in over 100 plants, especially in berries such as grapes. With the rise of the “French paradox”, resveratrol has attracted more and more attention from researchers. Recent studies have shown that resveratrol has a variety of biological activities and pharmacological effects such as antioxidant, anti-tumor and cardiovascular disease, and it can be used in medicine, food, cosmetics and health products and other fields. Because of the high cost of extraction from plants, the synthesis of resveratrol has attracted a lot of attention. The synthetic methods of resveratrol include biosynthesis and chemical synthesis. Among them, biosynthesis has a low yield and complex preparation, so chemical synthesis plays an important role in the synthesis of resveratrol. The methods of chemical synthesis of resveratrol mainly include Heck reation, Wittig reation, Perkin reaction, Suzuki reaction, organometallic reaction and so on. The synthesis of resveratrol was reviewed in order to promote the further development of resveratrol.

Key words: resveratrol; Perkin reation; Heck reaction; Wittig reaction; Suzuki reaction; organometallic reaction; synthesis

 

应用Ugi/Michael串联反应构建杂环化合物的研究进展

商天奕,刘琰*

(信阳农林学院 生物与制药工程学院,河南 信阳 464000

 

摘要:杂环化合物是许多天然产物和药物分子的核心骨架,具有广泛的生物活性和药理作用。因此如何快速高效地构建小分子杂环化合物库成为当今药物化学领域的研究热点。Ugi反应在合成分子多样性方面具有得天独厚的优势,能够解决待合成化合物数量庞大、结构复杂的难题;同时Michael加成反应能快速形成C—C/C—N键,从而构建出不同骨架的环系。目前,Ugi/Michael串联反应已经成为构建杂环化合物的有力工具。作者长期致力于应用Ugi串联反应构建具有潜在药理活性的杂环分子,将近年来Ugi/Michael串联反应的研究进展与课题组的研究工作相结合对这一领域进行综述。

关键词:Ugi反应;Michael加成;串联反应;杂环化合物

中图分类号:O6     文献标识码:A        文章编号:0258-32832019--

 

Recent Progress in Synthesis of heterocyclic Compounds by Ugi/Micheal tandem reaction SHANG Tian-yi, LIU Yan*(College of Biological and Pharmaceutical Engineering, Xinyang University of Agriculture and Forestry, Xinyang 464000, China), Huaxue Shiji, 2019, 41(9), ~


Abstract: Heterocyclics are the core structure of many natural products and drug molecules which have a wide range of biological and pharmacological activities. So efficient construction of heterocyclic compound libraries has become one of the research hotspots in the organic synthesis field. Ugi/Michael tandem reaction has been frequently used as a powerful tool to synthesize heterocyclic compounds, because Ugi reaction has unique advantages in generating molecular diversity to gain a large quantity of products with complex properties and Michael addition reaction can be established to construct heterocyclic ring system by the formation of C-C/C-N bond. Great efforts are made by the author's group to apply Ugi reaction cascade in building up heterocyclic molecules with potential pharmacological activities, therefore, in this paper, the recent progress in Ugi/Michael tandem reaction combined with research of our group is summarized.ng up heterocyclic molecules with potential pharmacological activities, therefore, in this paper, the recent progress in Ugi/Michael tandem reaction combined with research of our group is summarized.

Key words: Ugi reaction; Michael addition; tandem reaction; heterocyclic compounds.

 

 

有机催化靛红亚胺不对称Mannich反应

张俊伟,金瑛*,姜英子*

(延边大学 药学院,吉林 延吉 133000

 

摘要:3-氨基-2-吲哚酮骨架化合物在药物合成领域具有潜在应用价值。目前靛红亚胺参与不对称Manich反应是合成手性3-氨基-2-吲哚酮衍生物的有效方法之一。结合国内外近3年的文献报道,围绕着金鸡纳碱及其衍生物不对称催化、其他有机小分子不对称催化和有机金属不对称催化3个方面综述了靛红亚胺参与的不对称反应合成手性3-氨基-2-吲哚酮衍生物类化合物的研究进展。并对靛红亚胺参与的不对称催化合成3-氨基-2-吲哚酮骨架化合物进行了展望。

关键词:有机不对称催化;靛红亚胺;Mannich反应

中图分类号:O626.13     文献标识码:A   文章编号:0258-32832019--

 

Organic Asymmetric Catalyzed Mannich Reaction of isatin imine Zhang Jun-wei, Jin Ying*, Jiang Ying-zi* (School of Pharmacy, Yanbian University, Yanji 133000, China), Huaxue Shiji, 2019, 41(9),

AbstractThe 3-substituted 2-aminooxindoles skeleton compound has potential application value in the field of pharmaceutical synthesis. At present, the involvement of indole imine in the asymmetric Manich reaction is one of the effective methods for the synthesis of chiral 3-substituted 2-aminooxindoles derivatives. In this paper, combined with the literature reports in the past three years at local and abroad, the asymmetric asymmetry of cinchona and its derivatives, asymmetric catalysis of other small organic molecules and asymmetric catalysis of organometallics are reviewed. Research progress in the synthesis of chiral 3-amino-2-indolone derivatives. The asymmetric catalytic synthesis of 3-amino-2-indolone skeleton compounds in the presence of eosin was prospected.

Key words: Organic asymmetric catalysis; isatin imine; Mannich reaction

 

 

铜催化的硫叶立德和偶氮二甲酸酯的反应

周柄男,董军,许家喜*

(北京化工大学 化学学院 化工资源有效利用国家重点实验室,北京 100029

 

摘要:铜催化的酰甲基硫叶立德和偶氮二甲酸二乙酯反应,可以高效合成2-酰亚甲基肼-1,1-二甲酸二乙酯和3,6-二酰基-1,2,4,5-四氮杂环己烷-1,2,4,5-四甲酸四乙酯。通过控制温度实现了对两种产物的有效调控,在最优反应条件下,80 oC下以最高96%产率生成单一的肼二甲酸酯类化合物,室温条件下得到以四氮杂环己烷类化合物为主要产物的混合物,最高产率为55%。四氮杂环己烷化合物在加热条件下很容易转化成更稳定的肼类化合物,是制备2-酰亚甲基肼-1,1-二甲酸二乙酯和3,6-二酰基-1,2,4,5-四氮杂环己烷-1,2,4,5-四甲酸四乙酯类化合物的有效方法,具有原料简单易得和安全性高等优点

关键词:铜催化;硫叶立德;偶氮二甲酸酯;肼;四嗪

中图分类号:O623.7      文献标识码:A      文章编号: 0258-3283(2019)--

 

Copper-Catalyzed Reaction of Acylmethylide Sulfur Ylides with Dialkyl Azodicarboxylates

ZHOU Bing-nan, DONG Jun, XU Jia-xi* (State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China), Huaxue Shiji, 2019, 41(  ),

AbstractThe copper-catalyzed reaction of dimethylsulfoxonium acylmethylide sulfur ylides and diethyl azodicarboxylate afforded diethyl 2-acylmethylidenehydrazine-1,1-dicarboxylates and tetraethyl 3,6-diacylhexahydrotetrazine-1,2,4,5-tetracarboxylates efficiently. The major products of the reaction were effectively controlled by changing reaction temperature. Tetrazine products were the major products at room temperature with up to 55% yield, while hydrazine products were obtained only at 80 oC in refluxing 1,2-dichlorethane with up to 96% yield. Tetrazine products converted into more stable hydrazines easily under heating due to their instability. The synthetic methods are efficient routes for preparations of diethyl 2-acylmethylidenehydrazine-1, 1-dicarboxylates and tetraethyl 3, 6-diacylhexahydrotetrazine -1, 2, 4, 5 -tetracarboxylates with advantages of simple starting materials and high safety.

Key wordscopper-catalysis; sulfur ylide; azodicarboxylate; hydrazine; tetrazine

 

 

氨基醇催化氧化胺型查耳酮与炔的加成反应研究

徐嘉琪,夏曦,胡越高,陈煜,杨鸿均*,赵志刚,陈峰

(西南民族大学 化学与环境保护工程学院,四川 成都  610041)

 

摘要:吡啶-N-氧化物及其衍生物作为重要的氮杂环类化合物,在诸多领域中有着重要的应用价值,报道了以氧化胺型査耳酮为底物,N, N-二甲基乙醇胺为配体,苯乙炔为亲核试剂,进行1, 2加成反应,得到炔基醇类吡啶氮氧化物,收率高达98%。研究发现,反应对多种不同取代基的查耳酮底物均有较好的普适性,且反应产物结构中含有碳碳双键、碳碳三键、叔醇、吡啶氮氧基4个官能团,可进行多种途径的衍生。所有产物都经过1HNMR13CNMRHRMS鉴定。

关键词:氧化胺型查耳酮;苯乙炔;1, 2加成反应;氨基醇

中图分类号:O621. 3        文献标识码:A          文章编号:0258-32832019--

 

Study on the Addition Reaction of Amino Alcohol Catalyzed Amine Oxide Chalcone with Alkyne Xu Jia-qi, Xia Xi, Hu Yue-gao, Chen Yu, Yang Hong-jun, Zhao Zhi-gang, Chen Feng (College of Chemistry & Environment Protection Engineering, Southwest Minzu University, Chendu 610041, China), Huaxue Shiji, 2019, 41(9),

AbstractPyridine-N-Oxide and its derivatives, an nitrogen heterocyclic compound, have important application value in many fields. This paper have described a reaction with carried out to finally obtain the alkynol pyridine nitrogen oxide, which use the amine oxide type chalcone as the substrate, N, N-dimethylethanolamine as the ligand and phenylacetylene as the nucleophilic reagent. A series of substituted chalcone were applied to the reaction with up to 98% yield. These product contains carbon-carbon double bond, carbon-carbon triple bond, tertiary alcohol, pyridyl oxy group, which can be derivatized in various ways. All products were determined by 1H NMR, 13C NMR and HRMS techniques.

Key wordsamine oxide chalcones; phenylacetylene; 1, 2 addition reaction; amino alcohol

 

 

无金属条件下醚参与的烯烃双官能团化反应研究

 

艾先鸿, 李静, 谷利军*

(云南民族大学 民族药资源化学国家民族事务委员会

教育部共建重点实验室, 云南 昆明 650500

 

摘要:实现无金属条件下,醚参与的非活化烯烃烷杂芳基化反应。以过氧化苯甲酸特丁酯(TBPB)为自由基引发剂,通过自由基烯烃双官能团化反应,将醚和苯并噻唑环通过一步反应引入烯烃双键两端。结果表明,在优化条件下,四氢呋喃、1,4-二氧六环、乙醚及苯甲醚均能与含苯并噻唑环的非活化烯烃反应得到相应的产物。实现了无金属条件醚参与的非活化烯烃双官能团化反应,目标化合物用1HNMR13CNMRMSHRMS等进行了结构表征,以(4-苯并噻唑-2-取代)-5-(四氢呋喃-2-取代)-1-苯基戊烷-1-酮为例,分析了其波谱数据及反应机理。

关键词: 烯烃;双官能团化;无金属条件;合成

中图分类号: O657. 36     文献标识码: A    文章编号0258-3283201909--

 

Difunctionalization of Olefins Involved by Ethers under Metal-free Conditions AI Xian-hong, LI Jing, GU Li-jun* (Key Laboratory of Ethnic Medicine Resource Chemistry, State Ethnic Affairs Commission & Ministry of Education, Yunnan Minzu University, Yunnan 650500, China), Huaxue Shiji, 2019, 41(9),

Abstract : The direct difunctionalization of alkenes with simple alkyl ethers via distal heteroaryl ipso-migration has been accomplished under metal-free and neat conditions. Difunctionalization of alkenes via TBPB-catalyzed alkylheteroarylation between the C—C double bonds of benzothiazole-substituted tertiary alcohol and the α-C(sp3)-H bonds of ethers under metal-free conditions. It was found that the reactions of tetrahydrofuran, 1,4-dioxane, diethyl ether and anisole reacted smoothly with unactived olefin. A novel TBPB-catalyzed alkylheteroarylation via distal heteroaryl ipso-migration between the C—C double bonds of benzothiazole-substituted tertiary alcohol and the α-C(sp3)-H bonds of ethers have been developed. The desired products were characterized by 1HNMR, 13CNMR spectroscopy, MS and HRMS. The spectroscopic data of the target compound 3a was fully analyzed and the reaction mechanism is proposed.

Keywords : alkenes, difunctionalization, metal-free condition, synthesis

 

水相中微波辅助合成硫吡喃并喹啉衍生物

吴璐璐,姜松,安万凯,曹占奇,潘振良*

(河南农业大学 理学院,河南 郑州  450002)

 

摘要:硫吡喃并喹啉是一类非常重要的杂环骨架,具有多种显著的生物活性。报道了在微波辅助条件下,以水为溶剂,2-巯基喹啉-3-甲醛和a, b-不饱和醛为原料,经串联sulfa-Michael/aldol反应合成了15种不同取代的目标化合物。目标化合物的结构经核磁共振波谱(NMR)和高分辨质谱(HRMS)确证。克服了传统方法中有机溶剂对环境造成的污染,具有操作简单、收率高等优点,符合绿色化学理念。

关键词:微波辅助合成; 串联反应; 硫吡喃并喹啉; 绿色化学

中图分类号:0626.32+3         文献标志码:A      文章编号:0258-32832019--

Water-phase Synthesis of Thiopyrano[2,3-b]quinoline Derivatives under Microwave Irradiation WU Lu-lu, JIANG Song, AN Wan-kai, CAO Zhan-qi, PAN Zhen-liang* ( College of Science, Henan Agricultural University, Zhengzhou 450002, China)Huaxue Shiji, 2019, 41(9),

Abstract: Fifteen different substituted thiopyrano[2,3-b]quinolines were synthesized under microwave-assisted conditions by cascade reaction with 2-mercaptoquinoline-3-carbaldehyde and a, b-unsaturated aldehydes as the starting materials in water. The products were confirmed by nuclear magnetic resonance (NMR) spectroscopy and high resolution mass spectrometry (HRMS) data. Comparised with traditional method, the technology overcomes the environmental pollution caused by the use of organic solvent and has the advantages of easy operation and high yield, which conforms to the concept of green chemistry.

Key words: microwave-assisted synthesis; cascade reaction; thiopyrano[2, 3-b]quinoline; green chemistry

 

四氮唑锚定卟啉用于染料敏化太阳能电池

武彧*1,邹洪涛1,刘家成*2

(1.黔南民族师范学院 化学化工学院,贵州 都匀 558000

2.西北师范大学 化学化工学院,甘肃 兰州 730070

 

摘要:染料敏化太阳能电池(DSSCs)是利用太阳能进行开发光电转换的新型装置,受到人们广泛关注。将四氮唑基团作为染料敏化太阳能电池的锚定分子,具有共轭性强和较好的电子传递效应。研究了3种不同金属的四氮唑基团锚定,并对其合成、光学、电化学性能进行研究。结果表明锌四氮唑卟啉具有较好的光捕获性能,是用于太阳能电池的较优材料。

关键词:四氮唑卟啉;锚定;染料敏化太阳能电池

中图分类号O641.4         文献标识码A             文章编号0258-3283(2019)--

 

Tetrazolyl Horizontal Anchored Porphyrin for Dye-Sensitized Solar Cells WU Yu*1, ZOU Hong-tao1, LIU Jia-cheng*2(1. School of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China2.College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China), Huaxue Shiji, 41(  ),

AbstractDye-sensitized solar cells (DSSCs) are a new device for developing photoelectric conversion using solar energy, which has attracted wide attention. Tetrazole is used as anchoring group application in dye-sensitized solar cells which has strong conjugation and good electron transfer effect. Three different types of metal ions with tetrazole group anchored were investigated, and their synthesis, optical and electrochemical properties were investigated. The results showed that zinc tetrazolium porphyrin had good light capture performance and was confirmed to be an excellent material for DSSCs.

Key wordstetrazolium porphyrin; anchored; dye-sensitized solar cells

 

 

9-噻吨酮及其衍生物的聚集诱导发光性能研究

 

董玉叶1,2,贺佳2,梁辉2,潘成强2,籍少敏*2,霍延平*2,张欣*1

1.河北师范大学 化学与材料科学学院,河北 石家庄0500242.广东工业大学 轻工化工学院,广东广州510006

 

摘要:发现了化合物9-噻吨酮及其衍生物在水中有明显的聚集诱导发光(AIE)特性,并对其AIE发光性能进行了研究。发现其在水中能够引起聚集诱导发光,而在不良溶剂正己烷中没有发现聚集发光现象。通过溶剂化效应,排除了由于溶剂的极性不同而导致的发光强度不同。结合理论计算以及单晶结构确定,分子为平面构型。推测可能是由于,分子内的硫原子或羰基与水分子形成氢键或其他作用力,破坏了分子在聚集状态下的π-π堆积,使分子由聚集导致淬灭(ACQ)化合物转为AIE化合物。

关键词AIE;噻吨酮衍生物;π-π堆积;水

中图分类号O625.72        文献标识码A          文章编号:0258-32832019--

 

Aggregation-induced Emission Properties of 9-Thioxanthone Derivatives DONG Yu-ye1,2, HE Jia2, LIANG Hui2, PAN Cheng-qiang2, JI Shao-min*2, HUO Yan-ping*2, ZHANG Xin*1(1.College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China; 2. School of Chemicals Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China), Huaxue Shiji, 2019, 41(  ),

Abstract: Three thioxanthone-9-one 1 and its derivatives 2 and 3 were found to have aggregation-induced luminescence (AIE) behaviorsin water. The AIE properties were investigated systematically by fluorescence emission spectrum.Solvent effects experiment was carried out in order to exclude that the change of emission intensity of these compounds was due to the polarity of the solvent. The planar configuration of the molecules are determined by theoretical calculation. The formation of hydrogenbonds or other forces between sulfur atoms or carbonyl groups in the molecules with water may destroy the π-π stacking of molecules in the aggregated state, leading to thioxanthone-9-one 1and compounds 2 and 3 from ACQ compounds to AIE compounds.

Key words: AIE; thioxanthone derivatives; π-π stacking; water

 

 

磁改性生物质的固相热合成及其对甲基橙的吸附研究

 

牛静*,黄会彬,王利瑶,孙婉琪,张宁

(黄淮学院 化学与制药工程学院,河南驻马店 463000

 

摘要:实验利用过渡金属元素对生物质甘蔗渣进行改性,采用固相热处理法制备磁性复合材料,并对所得材料的形貌和所含官能团进行了TEMFTIR表征。以阴离子染料甲基橙为模型吸附染料,用吸附率作为评价指标,研究了改性元素种类、质量比、吸附剂用量、甲基橙初始浓度、溶液pH、温度以及时间等实验条件对复合材料吸附性能的影响。在优化的条件下,铁、镍磁改性吸附剂对甲基橙的吸附率达到92%。此外,吸附后的材料可方便地通过磁铁回收再利用。

关键词:固相热合成;磁改性生物质;甲基橙

中图分类号             文献标识码A             文章编码0258-32832019--

 

Magnetic Modified Biomass by Solid Thermal Synthesis and Adsorption of Methyl Orange Niu Jing*, Huang Hui-bin, Wang Li-yao, Sun Wan-qi, Zhang Ning (College of Chemistry and Pharmaceutical Engineering, HuangHuai University, Zhumadian 463000, China), Huaxue Shiji, 2019, 41(  ),

Abstract:The biomass bagasse was prepared by solid phase heat treatment using transition metals as magnetic modifier, and the obtained materials morphology and functional groups was characterized accordingly by TEM and FTIR. The composites performance was confirmed utilizing adsorption rateas evaluation index and methyl orange, as target molecules. The factors for composites performance such as species of elements, mass ratio, adsorbent dosage, initial concentration of methyl orange, pH of the solution, temperature and time were explored. Under optimized conditions, methyl orange adsorption rate reached 92% by the iron and nickel modified magnetic adsorbent. Furthermore, the adsorbent can be reused by magnetre cycling.

Key word: solid thermal synthesis; magnetic modified biomass; methyl orange

 

榴莲壳基多级孔炭材料的制备及其对染料吸附行为研究

 

程青,周月,黄琳娜,周全法,秦恒飞*

(江苏理工学院 化学与环境工程学院,江苏 常州  213001

 

摘要:以农林废弃物榴莲壳为原料,用KOH化学活化法制备榴莲壳基活性炭(DSAC),通过单因素分析法和正交试验得出最佳工艺条件,对有机染料亚甲基蓝和甲基橙进行吸附研究。结果表明:在炭化温度500,活化温度800 ºC,活化时间90 min,碱炭比3:1的条件下得到多级孔炭材料,比表面积达到了2975 m2/g,其微孔率为94%,介孔率为6%DSAC对亚甲基蓝吸附值高达315 mg/g。同时研究了DSAC对有机染料的吸附行为,实验表明其吸附等温模型更接近Langmuir吸附等温模型,吸附动力学更符合准二级动力学模型,吸附过程由液膜扩散和颗粒内扩散共同控制。

关键词:榴莲壳;正交试验;活性炭;有机染料

中图分类号:TQ9      文献标识码:A      文章编号:0258-3283(2019)

 

Preparation of Durian Shell-based Multistage Porous Carbon Materials for Dye Adsorption Behavior CHENG Qing, ZHOU Yue, HUANG Lin-na, ZHOU Quan-fa, QIN Heng-fei * (Department of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001, China), Huaxue Shiji, 2019, 41()

Abstract: The durian shell-based activated carbon (DSAC) was prepared by KOH chemical activation method using the laurel shell of agricultural and forestry waste. The best process conditions were obtained by single factor analysis and orthogonal experiment. The adsorption of organic dyes methylene blue and methyl orange was investigated. The results show that the multi-stage pore carbon material is obtained at a carbonization temperature of 500 ℃, an activation temperature of 800 ℃,an activation time of 90 min,and an alkali carbon ratio of 3:1. The specific surface area is 2975 m2/g, and the micro porosity is 94%. The meso-porosity is 6%. DSAC has an adsorption value of methylene blue of up to 315 mg/g. At the same time, DSAC elucidated the adsorption behavior of organic dyes. The experimental results show that the adsorption isotherm model is closer to the Langmuir adsorption isotherm model, and the adsorption kinetics is more in line with the quasi-secondary kinetic model. The adsorption process is controlled by liquid membrane diffusion and intra-particle diffusion.

Key words: durian shell; orthogonal experiment; activated carbon; organic dyes

 

 

过渡金属参与的联苯烯衍生物碳-碳键活化反应的研究进展

尚鑫1,董振飞2,刘澜涛*1, 2,卢会杰*1

(1.      郑州大学 化学与分子工程学院,河南 郑州  4500002.商丘师范学院 化学化工学院,河南 商丘  476000)

 

摘要:碳-碳键的活化反应具有原子经济性和步骤简便性,可以从简单易得的原料合成复杂的有机分子。由于联苯烯化合物中含有较大环张力的四元环结构,联苯烯类衍生物能够与低价金属发生氧化加成反应,从而生成金属杂五元环中间体,生成的金属杂五元环中间体可与多种底物进一步发生反应,生成环状有机化合物;此外还可以高效催化其他反应。综述了由过渡金属(NiIrRhPdAuPt)与联苯烯类衍生物氧化加成反应而引发的碳-碳键活化反应的研究进展。

关键词:过渡金属;联苯烯;氧化加成;碳-碳键活化

中图分类号:O62                文献标识码:A           文章编号:0258-32832019

 

Recent Advances of C-C bond Activation of Biphenylenes with Transition-metals SHANG Xin1, DONG Zhen-fei2, LIU Lan-tao1,2, LU Hui-jie*1 ( 1.College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450000, China; 2.College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, China), Huaxue Shiji, 2019, 41()

AbstractThe C-C bond activation process presents a highly atom, and step economical access to complex organic molecules from readily available simple starting materials. Due to the high strain energy arising from the four membered ring moiety, the oxidative additions of biphenylenes to the low-valent metals tend to occur generating five membered metallocycles which can go on to give various products or serve as catalysts for other reactions. The review focuses on C-C bond activation of biphenylenes triggered by their oxidative additions to the low-valent metalsNiIrRhPdAuPtand their application in organic synthesis.

Key wordstransition metalbiphenyleneoxidative additionsC-C bond activation

 

 

PEI包裹的Mn掺杂ZnS量子点检测氨苄西林

张国贤,赵亮,许强,栗东霞,雒旭艳,刘帅,闫桂琴*

(山西师范大学 生命科学学院,山西 临汾  041000

摘要:以水相法合成了聚乙烯亚胺(PEI)包裹的Mn掺杂ZnS量子点(PEI-Mn/ZnS·QDs),基于氨苄西林(Amp)与量子点表面氨基之间的氢键作用和静电作用,使PEI-Mn/ZnS·QDs的室温磷光(RTP)增强,建立了一种简便快速的Amp室温磷光检测方法。在最佳实验条件(pH7.4,反应10 min)下,PEI-Mn/ZnS·QDsRTPCAmp之间线性相关方程为P/P00.007 CAmp+1.076,线性范围为0.04180 μmol/L,相关系数R0.994,检出限为0.013 μmol/L。相比于其他方法,该方法检测范围宽,检出限低,并且无需外加氧化剂和复杂的预处理,同时可以有效避免生物体液的自体荧光干扰。最后将该方法用于牛奶与生物体液中Amp的检测,加标回收率为90%~103.6%,结果满意。

关键词:聚乙烯亚胺,量子点(QDs),室温磷光,氨苄西林

中图分类号: O657.3      文献标识码: A     文章编号:0258-32832019--

 

Room Temperature Phosphorescence Detection of Ampicillin by PEI-Mn/ZnS Quantum Dots ZHANG Guo-xian, ZHAO Liang, XU Qiang, LI Dong-xia, LUO Xu-yan, LIU Shuai, YAN Gui-qin* (College of Life Sciences, Shanxi Normal University, Linfen 041000, China), Huaxue Shiji, 2019, 41(  ),

Abstract: PEI-Coated Mn-doped ZnS quantum dots (PEI-Mn/ZnS·QDs) were synthesized by aqueous phase method. Based on the hydrogen bonding and electrostatic interaction between ampicillin (Amp) and -NH3+ which was modified on the surface of PEI-Mn/ZnS·QDs, the room temperature phosphorescence (RTP) of PEI-Mn/ZnS·QDs was enhanced, establishing a simple and rapid Amp RTP detection method. Under the optimal experimental conditions (pH7.4, 10 min), the detection linear correlation equation between RTP of QDs and CAmp is P/P0 0.007 CAmp1.076, whose linear range is 0.04180 μmol/L. The correlation coefficient of is R0.994, the relative standard deviation (RSD) is 2.6%, and the detection limit is 0.013 μmol/L. Compared with other methods, the method has a wide detection range, low detection limit, and don’t need external oxidant and complicated pretreatment, as well as can effectively avoid autofluorescence interference of biological fluid. Finally, the method was applied to the detection of Amp in milk and biological fluids, and obtained with satisfactory results: recoveries of spiked samples were lying in 90%103.6%.

Key words: polyethyleneimine; quantum dots; room temperature phosphorescent; ampicillin

 

 

磁性分散固相萃取/ECD-GC同时检测家禽、畜肉中有机氯和菊酯类农药残留

李桂琴1,王晓莉*2

1. 兴安职业学院,内蒙古 乌兰浩特  1374002. 内蒙古化工职业学院,内蒙古 呼和浩特  010070

摘要:建立了气相色谱法对家畜、禽肉样品中的有机氯和菊酯农药残留进行同时检测的方法。样品经过一种新型的磁性分散固相萃取技术---Fe3O4/AMWNTs磁性材料进行超声提取、乙腈解析20 min、净化以及浓缩,然后进行气相色谱-ECD检测器分析,外标法定量。结果表明农药残留的分离度好,线性关系良好,相关系数均>0.999RSD<5%,实际样品检出率在75% 95%之间。此方法灵敏度高、操作快速、简便、净化彻底,回收率在94.5% 99.1%之间,结果令人满意,此方法可适用于肉类产品中有机氯和菊酯类农药残留的筛查及定量检测。

关键词:家禽;畜肉;有机氯和菊酯类农药残留;磁性分散固相萃取;ECD-GC

中图分类号:0657.7          文献标识码:A              文章编号:0258-32832019

 

Simultaneous Detection of Organochlorine and Pyrethroid Pesticide Residues in Poultry and livestock meat by Magnetic Dispersion Solid phase Extraction/ECD-GC LI Gui-qin1WANG Xiao-li*2 (1. Xing An Vocational and Technical College, Ulanhot 137400, China2. Inner Mongolia Vocational College of Chemical Engineering, Hohhot 010070, China ), Huaxue Shiji, 2019, 41()

Abstract: To determine the residues of organochlorine and pyrethroid pesticides in livestock and poultry. Simultaneously detected organochlorine and pyrethroid pesticide residues in samples by gas chromatography. A new tape of magnetic dispersed solid phase extraction technique was used to extract, purify, and concentrate the target substance, and then gas chromatography was carried out. The results show that the separation of pesticide residues and the linear relationship are good. The RSD is less than 5%, and the actual sample detection rate is between 75% and 95%. This method has high sensitivity, fast and simple operation, complete purification, and the recovery rate is between 94.5% and 99.1%.The results are satisfactory.

Key words: poultrylivestockorganochlorine and pyrethroid pesticide residuesmagnetic dispersion solid phase extractionECD-GC

 

EGFR单克隆抗体稳定性的影响因素研究

裴朝玉*,贠琳,袁萍,郭宇 

(周口师范学院 化学化工学院,河南 周口  466001

摘要:探讨了影响单克隆抗体稳定性的物理和化学因素。蛋白质浓度影响抗体稳定性,蛋白质浓度增加到一定值时,聚集体和降解片段含量都会增加,样品中高含量的聚集体会进一步促进抗体聚集。制剂pH影响抗体的稳定性,组氨酸缓冲液更有利于保持抗EGFR单克隆抗体制剂稳定性。制剂中聚山梨醇酯20可有效抑制聚集。结果表明:抗EGFR单克隆抗体稳定性的影响因素有蛋白质浓度、样品纯度、环境温度、缓冲液类型、溶液离子强度、溶液pH、表面活性剂。

关键词:抗人EGFR单克隆抗体;体积排阻色谱;离子交换色谱;SDS-PAGE;表面电荷异质性

中图分类号:R917    文献标识码:A    文章编号:0258-32832019

 

The Impact Factors on anti-EGFR Monoclonal Antibody Stability

PEI Chaoyu YUN LinYUAN Ping ,  GUO Yu

(School of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhoukou 466001,China)

AbstractPhysical and chemical impact factors on anti-EGFR monoclonal antibody stability wan investigated. The results showed that: (1) when protein concentration was increased to some extent, monoclonal antibody produced aggregation and degradation; (2) aggregation could further happened with aggregates content in sample solution increased; (3) monoclonal antibody stability was affected by solution pH; (4)compared with two other buffers, histidine buffer could keep monoclonal antibody more stable; (5) polysorbate 20 in solution could effectively inhibit monoclonal antibody aggregation. The conclusion manifested that the stability of human anti-EGFR monoclonal antibody was affected by those factors including protein concentration, protein purity, surrounding temperature, buffer, ion strength of solution, buffer pH, surfactants.

 

Keywords: Human Anti-EGFR Monoclonal Antibody ; Size Exclusion Chromatography ; Ion Exchange Chromatography ; SDS-PAGE ; Surface Charge Heterogeneity

 

橘子皮生物质吸附废水中硫化物的性能研究

马艳梅

(信阳学院 理工学院,河南 信阳  464000

摘要:以橘子皮生物质为原料,以硫化钠溶液作为模拟含硫废水,研究橘子皮生物质对硫化物的吸附效果。探究吸附时间、用量、化学改性剂、pH及温度对其吸附效果的影响。研究发现,橘子皮生物质对废水中的硫化物有一定的吸附效果,在实验范围内,最佳吸附时间为6 h,最佳用量为20 g/L,最佳化学改性剂为NaCl,最佳溶液pH8,最佳吸附温度在30 ℃。结果表明橘子皮生物质对硫化物的吸附符合准二级动力学方程。

关键词:橘子皮;吸附;硫化物

中图分类号O69          文献标识码:A          文章编号:0258-32832019

 

Study on the adsorption performance of orange peel biomass on sulfide in wastewater Ma Yanmei School of Science and Technology, Xinyang College , Henan Xinyang, 464000, China

Abstract: Take orange peel biomassOPBas raw material, sodium sulfide solution was used to simulate sulfide wasterwater. The effects of time, amount of OPB, different substances, solution pH, temperature on the adsorption properties of sulfide from aqueous solution were investigated. The study found that the OPB has a certain adsorption effect on water sulfide. Within the scope of the experiment, The optimum temperature was 6 hour, the optimum input ratio was 20 g/L, the optimum modifier was NaCl, the optimum solution pH was 8 and the optimum temperature was 30, The results show that adsorption of OPB to sulfide conforms to the quasi-second order kinetics equation.

Key wordsorange peeladsorptionsulfide

 

 

一种酰腙类荧光探针的合成及其对Al3+的识别性能研究

龙昭现a,江光奇*a, b

(贵州大学 a.化学与化工学院, b.精细化工研究开发中心绿色农药和农业生物工程教育部重点实验室,贵州 贵阳  550025

 

摘要:1,2,4,5-四溴甲基苯和2,4-二羟基苯甲醛为反应原料,通过两步合成反应得到一种新型的酰腙类荧光探针。该化合物在VDMSO)∶V(水)=191的溶剂中对Al3+具有较好的选择性,在446 nm波长处有明显的荧光增强作用。通过Job法、核磁滴定、质谱分析表明,探针与Al3+的配合比为1:2,由光谱滴定实验可知,探针对Al3+的最低检出限为1.16×10-7 mol/L,其配合常数为2.28×103 L/mol。此外,实际应用研究表明,该荧光探针可以用于自来水和河水中一定浓度范围内Al3+的检测。

关键词:酰腙;荧光探针;铝

中图分类号:O614.3         文献标识码:A        文章编号:0258-32832019

 

Synthesis of Acylhydrazone based Fluorescent Probe for Al() and Its Property LONG Zhao-xiana, JIANG Guang-qi*a,b (a. College of Chemistry and Chemical Engineering, b. State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering of Ministry of Education, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2019, 41( )

Abstract: An acylhydrazone based fluorescent probes was synthesized by two-step reaction with tatrakis(bromomethyl)benzene and 2,4-dihyoxybenzaldehyde as raw materials. The compound showed excellent selectivity for Al3+ in the VDMSO)∶V(水)=191 solution, showing remarkable fluorescence enhancement effects towards Al3+ at the emission wavelength of 446nm.The stoichiometry of 12 of the Al() complexes were determined by Job’s plots, 1HNMR titration experiments and LC-MS analysis. The spectroscopic titration indicated that the detection limits of the probe for Al3+ was 1.16×10-7mol/L and the complexing constant of the probe to Al3+ was 2.28×103 L/mol. Furthermore, the probe can be used for the determination of Al3+ in the river water and tap water samples.

Key words: acylhydrazone; fluorescent probe; aluminum

 

基于磁分离方法的猪胰岛素受体分离与活性分析

钟王磊a,陈维娴a,周国华*b

(岭南师范学院 a. 生命科学与技术学院,b. 化学化工学院 清洁能源材料化学广东普通高校重点实验室, 广东 湛江  524048

 

摘要:目前,胰岛素受体的分离提取方法为凝集素亲和层析与以胰岛素作为配体的亲和层析。建立磁分离法,采用胰岛素受体亲和磁分离探针提取受体蛋白,对提取条件进行优化,并以免疫印迹法检测胰岛素作用下受体蛋白酪氨酸的自磷酸化反应。结果表明,磁分离探针与粗提取总蛋白孵育16 h是提取受体蛋白的较优条件,所得胰岛素受体保持了其生物活性,能够发生自磷酸化反应。这些结果表明磁分离方法可应用于胰岛素受体的分离纯化,该方法简便、特异性强、稳定、可靠,为胰岛素信号传导、糖尿病病理、药物筛选等研究提供了有效的研究工具。

关键词:胰岛素受体;磁分离;提取;信号传导;自磷酸化

中图分类号:Q5-33              文献标识码:A             文章编号:0258-32832019

 

Separation Based on Magnetic Probes and Activity Identification of Insulin Receptor in Liver of Pig ZHONG Wanglei1, CHEN Weixian1, ZHOU Guohua *2 (1. Life Science & Technology School, Lingnan Normal University, Zhanjiang 524048, China; 2. School of Chemistry and Chemical Engineering, Key laboratory of Clean Energy Materials Chemistry of Guangdong Higher Education Institutes, Lingnan Normal University, Zhanjiang 524048, China)

Abstract: At present, lectin affinity chromatography and insulin affinity chromatography are two main methods of separation and purification of Insulin receptor proteins. In this study, we designed a magnetic separation probe to isolate and purify insulin receptors and tested the biological activity of the extracted receptor proteins. Receptor protein was extracted by insulin receptor affinity magnetic separation probe, and the concentration of receptor protein extracted under different conditions was compared. The tyrosine auto-phosphorylation of receptor protein with insulin stimulus was detected by western blotting. The results showed that 16 hours of incubation between the magnetic separation probe and the total protein was the best condition for extracting the receptor protein. The tyrosine auto-phosphorylation of insulin receptor showed that the isolated insulin receptor has biological activity and can be used for further study of insulin signal transduction. Therefore, the magnetic separation method can be applied to the separation and purification of insulin receptor.

Key words: Insulin receptor; Magnetic separation; Purification; Signal transduction; Auto-phosphorylation

 

白车轴草多酚提取工艺优化

朱淼,廖文,向红,翁贵英,李欣燃,王绪英*

(六盘水师范学院 生物科学与技术学院,贵州 六盘水 553004

摘要:采用响应面法研究超声辅助提取白车轴草多酚工艺。先以白车轴草的茎、叶和花为原料,利用超声辅助法分别提取上述部位总多酚,并进行含量检测。结果表明白车轴草的花中多酚含量最高。再通过单因素试验考察提取液乙醇体积分数、提取时间和料液比对超声辅助提取白车轴草花中多酚得率的影响。以此为基础,采用响应曲面法优化白车轴草花中多酚提取工艺。结果表明,白车轴草花中多酚提取的最佳工艺参数为料液比168g/mL),提取时间43min,乙醇体积分数为43%。在此条件下,多酚得率为2.55%,与预测得率2.51%相近,且相对标准偏差为1.57%

关键词:白车轴草;多酚;提取

中图分类号Q946.8        文献标识码A       文章编号0258-32832019--

 

Optimization of Extraction Process of Polyphenol from Trifolium repens Linn ZHU Miao, LIAO Wen, XIANG Hong, WENG Gui-ying, LI Xin-ran, WANG Xu-ying* (School of Biological Sciences and Technology, Liupanshui Normal University, Liupanshui, 553004) Huaxue Shiji, 2019, 41(9),

Abstract Response surface methodology was used to study the ultrasonic-assisted extraction of polyphenols from Trifolium repens L. The ultrasonic-assisted method was used to extract total polyphenols in the stem, leaf, and flower of Trifolium repens L., and the content was detected. The results showed that the polyphenol content in the flowers was the highest. Single factor experiments investigated the effects of ethanol concentration, extraction time, and solid-liquid ratio on the extraction rate of polyphenols from Trifolium repens L. flower. On this basis, response surface methodology was used to optimize the extraction process of polyphenols. The results indicated that the optimum technological parameters for polyphenol extraction were the solid-liquid ratio of 1: 68 (g/mL), extraction time of 43min, and ethanol volume fraction of 43%. Under these conditions, the yield of polyphenol was 2.55%, which was close to the predicted return of 2.51%, and the relative standard deviation was 1.57%.

Keywords: Trifolium repens Linn; polyphenol; extraction

 

6,7,-二甲基-4-喹啉羧酸的合成

马兰兰a, b,罗大礼a, b,乐意a, b,黄筑艳*a, b

(贵州大学 a. 药学院,b. 贵州省合成药物工程实验室,贵州 贵阳 550025

 

摘要:喹啉类化合物是一类重要的医药及农药中间体。目标化合物的合成方法目前无文献报道,以3, 4-二甲基苯胺、水合氯醛和盐酸羟胺为起始原料,经酰胺化、环合、普菲青格反应和脱羧4步反应首次合成目标化合物,其结构经1HNMR13CNMRMS确证。路线具有原料廉价易得、反应条件温和、操作简单、后处理方便且收率较高等优点,适合工业化生产。

关键词:6, 7-二甲基-4-喹啉羧酸;3, 4-二甲基苯胺;合成

中图分类号:O626.13      文献标识码A         文章编号:0258-3283(2019)--

 

Synthesis of 6,7-Dimethyl-4-quinolinecarboxylic Acid MA Lan-lan a, b, LUO Da-li a, b, LE Yi a, b, HUANG Zhu-yan* a, b (a. School of Pharmaceutical Sciences, b. Guizhou Engineering Laboratory for Synthetic Drugs, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 41(9),

Abstract: Quinoline compounds are an important class of pharmaceutical and pesticide intermediates. The target compound has not been reported in the literature. 3, 4-Dimethylaniline, chloral hydrate and hydroxylamine hydrochloride are used as starting materials, and amidation and cyclization are carried out. The target compound was synthesized for the first time by Pfitzinger reaction and decarboxylation. The structure was confirmed by 1HNMR, 13CNMR and MS. It is easy to operate and control the reaction and the reaction conditions were mild and the yield was higher in each step with the convenient post-processing, which is suitable for industrial production.

Key words: 6, 7-dimethyl-4-quinolinecarboxylic acid; 3,4-dimethylaniline; synthesis