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《化学试剂》2022年第11期中英文摘要(附整期文章PDF文档)

【综述与专论】

沸石分子筛绿色高效合成的研究进展

吴春洋王知微赵莹张红丹*程鹏

(沈阳师范大学 化学化工学院 能源与环境催化研究所, 辽宁 沈阳  110034)

 

摘要:沸石分子筛是一类多孔材料,因其具有有序的孔道结构、高的水热稳定性以及独特的催化活性,作为一种优异的固体催化剂广泛应用于化学工业中。沸石分子筛在制备过程需要使用含硅、铝的化工原料以及价格昂贵且有毒害的有机模板剂。投入使用前需要通过煅烧去除有机模板剂,不但会产生污染环境的NOX化合物与温室气体CO2,而且会提高分子筛的合成成本。此外,沸石分子筛的晶化时间长达数天,造成极大能源损耗。因此,如何绿色高效地合成沸石分子筛材料意义重大。主要从合成原料和合成方法两方面阐述沸石分子筛的绿色高效合成,就其存在问题进行讨论,并对其未来发展进行展望。

关键词: 沸石分子筛;晶化;合成原料;羟基自由基辅助合成;微波辅助合成;无有机模板剂合成;无溶剂合成

中图分类号:TQ424.25               文献标识码: A           文章编号:0258-32832022

 

Research Progress of Green and Efficient Synthesis of Zeolite WU Chun-yang, WANG Zhi-wei, ZHAO Ying, ZHANG Hong-dan*, CHENG Peng (Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China) , Huaxue Shiji202244 (12)00 ~ 00

Abstract: Zeolite is a kind of porous materialwhich is widely used in chemical industry as an excellent solid catalyst due to its ordered pore structure, high hydrothermal stability and unique catalytic activity. Expensive and toxic organic templates as well as chemical raw materials containing silicon and aluminum are necessary in the synthesis of zeolite. Before usage, the organic templates need to be removed by calcination, which will not only produce NOx and greenhouse gas CO2, but also increase the synthesis cost of zeolite. In addition, the crystallization time of zeolite is up to several days, resulting in great loss of energy. Therefore, it is significant to synthesize zeolite via a green and efficient method. From two aspects of synthetic raw materials and synthetic methods to expounded the green and efficient synthesis of zeolite, discussing its existing problems and prospecting its future development.

Keywords: zeolite; crystallization; synthetic raw materials; hydroxyl radical-assisted synthesis; microwave-assisted synthesis; organotemplate-free synthesis; solvent-free synthesis

引用本文:吴春洋,王知微,赵莹,等. 沸石分子筛绿色高效合成的研究进展[J]. 化学试剂,202244(11): 1543-1550.

 

 

香芹酚及其衍生物的生物活性研究概述

韩维玲,张冬城,王江河,贺银菊,陈阔,彭莘媚*

(黔南民族师范学院 化学化工学院,贵州 都匀  558000)

摘要:香芹酚存在于多种植物中,早期主要应用为食品添加剂、香料、抗氧剂、驱虫剂及卫生杀菌剂。因其分子量小、结构简单、脂溶性高、生物活性多样、低毒副作用及临床耐受性好等特点逐步被广大医药研究者关注,其衍生物的获得与生物活性研究越来越多。基于近些年香芹酚及其衍生物在国内外的研究概况,综述了其在抗菌、抗氧化、抗癌、抗神经系统疾病及抗寄生虫等方面的生物活性研究进展,为香芹酚类化合物的进一步医药应用与开发提供参考

关键词:香芹酚;抗菌;抗氧化;抗癌;抗神经系统疾病;抗寄生虫

中图分类号:R914.4      文献标识码:A       文章编号:0258-32832022--

 

Research Overview on the Bioactivity of Carvacrol and its Derivatives HAN Wei-ling, ZHANG Dong-cheng, WANG Jiang-he, HE Yin-ju, CHEN Kuo, PENG Xin-mei* (School of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China), Huaxue Shiji, 2022, 44(11),

Abstract: Carvacrol exists in a variety of plants and was mainly used as food additive, spices, antioxidant, insect repellent and sanitary fungicide in the early stage. Due to the small molecular weight, simple structure, high lipid solubility, diverse biological activities, low-toxic side effects and good clinical tolerability etc., carvacrol has gradually attracted the attention of medical researchers. More and more studies have been made on the preparation and biological activity of carvacrol derivatives. Based on the research situation of carvacrol and its derivatives at home and abroad in recent years, the research progress of its biological activities mainly in antibacterial, antioxidant, anti-cancer, anti-nervous system diseases and anti-parasite aspect was reviewed. It is hoped to provide reference for further medical application and development of carvacrol and its derivatives.

Key words: carvacrol; antibacterial; antioxidant; anticancer; anti-nervous system disease; anti-parasite

引用本文:韩维玲,张冬城,王江河,等. 香芹酚及其衍生物的生物活性研究概述[J]. 化学试剂,2022,44(11):1551-1557.

 

 

分子印迹酶的研究现状及进展

金久煜a,b,c,李兆周*a,b,c,陈秀金*a,b,c,王耀a,b,c,李芳a,b,c,高红丽a,b,c,牛华伟a,b,c,于慧春a,b,c,袁云霞a,b,c,殷勇a,b,c

(河南科技大学a. 食品与生物工程学院b. 食品加工与安全国家级实验教学示范中心c. 河南省食品绿色加工与质量安全控制国际联合实验室,河南 洛阳  471000)

摘要:天然酶催化效率高、特异性强、反应条件温和,但对极端环境耐受性差、成本高、制备过程复杂。分子印迹聚合物是一类新兴的富集材料,具有广阔的应用前景。基于分子印迹材料构建模拟酶具有构象预定性、识别专一性、广泛适用性和制备便捷性,已成为研究的热点领域。概述了分子印迹模拟酶的构建途径,总结了分子印迹模拟酶的最新制备方法,介绍了新型分子印迹模拟酶的研究进展及应用,分析了其中的理论和技术问题,最后对分子印迹模拟酶的发展趋势进行了展望。所述内容有助于充实高效印迹酶的构建理论,发展新型制备方法,促进人工模拟酶的进一步推广应用。

关键词:分子印迹;模拟酶;制备;应用进展

中图分类号:0631           文献标识码:A       文章编号:0258-32832022--

 

Research Status and Progress of Molecularly Imprinted Enzymes JIN Jiu-yu a,b,c, LI Zhao-zhou *a,b,c  ,CHEN Xiu-jin* a,b,c , WANG Yao a,b,c, LI Fang a,b,c, GAO Hong-li a,b,c, NIU Hua-wei a,b,c, YU Hui-chun a,b,c, YUAN Yun-xia a,b,c, YIN Yong a,b,c (a. College of Food and Bioengineering, Henan University of Science and Technology, b. National Demonstration Center for Experimental Food Processing and Safety Education, c. Henan International Joint Laboratory of Food Green Processing and Quality Safety Control, Luoyang 471000, China), Huaxue Shiji, 2022, 44(11),

AbstractNatural enzyme has high catalytic efficiency and specificity with gentle reaction conditions. However, it can not work in extreme environments, expensive, and the preparation process is complicated. Molecularly imprinted polymer is a kind of enrichment material that has wide application. With the properties of predetermined conformation, specificity of recognition, wide applicability, and ease of preparation, the mimic enzymes based on molecularly imprinted materials have becomed a research hotspot. The review outlined the construction pathways of molecularly imprinted enzymes, summarized the new preparation methods, introduced the research progress and application of new molecularly imprinted enzymes, and analyzed the theoretical and technical problems. Finally, the development prospects of molecularly imprinted enzymes were proposed. The review will enrich the construction theory of high-efficiency imprinting-enzymes, develop novel preparation methods, and promote the application of artificial mimic enzymes.

Key wordsmolecular imprinting; mimic enzyme; preparation; application progress

引用本文:金久煜,李兆周,陈秀金,等. 分子印迹酶的研究现状及进展[J]. 化学试剂,202244(11): 1558-1567.

 

 

镍催化叔烷基亲电试剂参与碳碳键还原偶联反应研究

高楠星,滕大为*

(青岛科技大学 化工学院,山东 青岛  266042)

 

摘要:镍金属催化的还原偶联反应可直接利用来源广泛、价格低廉的亲电试剂作为偶联底物,具有反应条件温和、能允许反应中存在少量水和空气、官能团兼容性好等优点。含有季碳结构的化合物广泛存在于多种药物和生物活性的分子中。叔烷基亲电试剂由于空间位阻大、反应活性低、在反应中容易生成其他副产物,作为底物参与还原偶联反应仍具挑战。综述了近十年关于叔烷基亲电试剂作为底物参与的碳碳键还原偶联反应研究进展,讨论了不同催化反应中底物范围及机理。

关键词:镍催化;叔烷基亲电试剂;亲电试剂;还原偶联反应;季碳化合物

中图分类号:O621.3    文献标识码:A       文章编号:0258-32832022

 

Nickel-catalyzed Carbon-carbon Bond Formation via Reductive Couplings of Tertiary Alkyl Electrophiles GAO Nan-xing, TENG Da-wei *(College of Chemistry Engineering, Qingdao University of Science and Technology, Qingdao 266042, China) , Huaxue Shiji202244 (11)00 ~ 00

AbstractThe nickel-catalyzed reductive coupling could directly use a wide range of inexpensive electrophiles as the coupling substrates, which has the advantages of mild reaction conditions, water- and air- insensitive, and shows good tolerance to functional groups. All-carbon quaternary scaffolds are prevalent in drugs and biologically active molecules. As a result of the high steric hindrance, low reactivity, and tendency to generate byproducts in the reactions, it is a challenge for the transformation of tertiary alkyl electrophiles in reductive couplings. Summarized the research progress in recent ten years of nickel-catalyzed carbon-carbon bond-forming reductive couplings, which involving the tertiary alkyl electrophiles as the substrates. The range of substrates and mechanisms of different catalytic systems were discussed.

Key wordsnickel-catalyzed; tertiary alkyl electrophile; electrophile; reductive coupling; quaternary carbon compound

引用本文:高楠星,滕大为. 镍催化叔烷基亲电试剂参与碳碳键还原偶联反应研究[J]. 化学试剂,202244(11): 1568-1576.

 

 

【生化与药用试剂】

载刺五加/桂皮紫萁海藻酸钠/羧甲基壳聚糖水凝胶伤口敷料的制备及其性能研究

张莉弘,窦信,邱鹏,刘通,勾东霞*,赵珺

(长春大学 食品科学与工程学,吉林 长春  130118

 

摘要:为设计一种对伤口无损伤、抑菌抗炎效果好的伤口敷料,选择海藻酸钠(SA)与羧甲基壳聚糖(CMCS)为原料,通过抗拉伸强度优化SA/CMCS水凝胶的制备条件;然后添加刺五加/桂皮紫萁提取物,制备载刺五加/桂皮紫萁SA/CMCS水凝胶伤口敷料,并对其性质和功能进行研究。结果表明,SA/CMCS水凝胶最佳制备工艺为NaCl浓度0.8%1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐/N-羟基琥珀酰亚胺(EDC/NHS)添加量2.25%mSA)∶mCMCS=11,此时抗拉伸强度为0.884 MPa。红外光谱分析表明SACMCS为化学交联。载刺五加/桂皮紫萁SA/CMCS水凝胶伤口敷料孔隙率为(90.5±1.2%,溶胀度为(133±2.7%,药物累计释放率为(93.34±2.4%,且具有良好缓释作用、抑菌抗炎性和生物相容性。制备的载刺五加/桂皮紫萁SA/CMCS水凝胶伤口敷料是一种良好的伤口敷料。

关键词:羧甲基壳聚糖;海藻酸钠;水凝胶;刺五加/桂皮紫萁提取物;伤口修复

中图分类号:R313                              文献标识码:A                             文章编号:0258-32832022--

 

Study on the Preparation and Properties of Acanthopanax senticosus/Cinnamomum cassia-Loaded Sodium Alginate-carboxymethyl Chitosan Hydrogel Wound Dressing ZHANG Li-hong, DOU Xin, QIU Peng, LIU Tong, GOU Dong-xia*, ZHAO Jun (College of Food Science and Engineering, Changchun University, Changchun 130118, China), Huaxue Shiji, 2022, 44(11)

Abstract:: In order to design a wound dressing that does not damage to the wound, have good anti-bacterial and anti-inflammatory effect, sodium alginate (SA) and carboxymethyl chitosan (CMCS) were selected as raw materials, the preparation conditions of SA/CMCS hydrogel were optimized by tensile strength; Acanthopanax senticosus/Cinnamomum cassia extraction was compounded into hydrogel, to make Acanthopanax senticosus/Cinnamomum cassia-loaded SA/CMCS hydrogel wound dressing, the properties and functions were studied. The results showed that the optimal preparation process of SA/CMCS hydrogel was 0.8% NaCl, 2.25% EDC/NHS, mSA)∶mCMCS=11, under this condition, the tensile strength was 0.884 MPa. Infrared spectroscopy analysis showed that SA and CMCS was chemical cross-linking; the porosity of Acanthopanax senticosus/Cinnamomum cassia loaded SA/CMCS hydrogel was 90.5 ± 1.2%, the swelling was 133 ± 2.7%, the ratio of drug release was 93.34±2.4%. At the same time, it showed good sustained release effect, antibacterial and anti-inflammatory effects, and excellent biocompatibility, as well. The results showed that the prepared Acanthopanax senticosus/Cinnamomum cassia-loaded SA-CMCS hydrogel could be used as a good wound dressing material.

Key words: carboxymethyl chitosan; sodium alginate; hydrogel; Acanthopanax senticosus/Cinnamomum cassia extraction; wound repair

引用本文:张莉弘,窦信,邱鹏,等. 载刺五加/桂皮紫萁海藻酸钠/羧甲基壳聚糖水凝胶伤口敷料的制备及其性能研究[J]. 化学试剂, 2022, 44(11): 1577-1584.

 

 

具有生物活性的脱氢枞胺衍生物研究进展

黄静玲,梁锦萍,周凤姬,何金芝,张振伟,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  530200)

摘要:脱氢枞胺是松香的重要改性物质之一,也是歧化松香胺的主要成分,分子中具有稳定的手性三环菲结构和可修饰的胺基,可以与生物大分子进行手性识别,是一类重要的药性骨架。其衍生物具有抗菌、抗病毒、抗癌等多种生物活性,可作为先导化合物用于新药发现。以脱氢枞胺衍生物展现出的生物活性为依据进行分类,介绍近年来具有生物活性的脱氢枞胺衍生物的研究进展,以期为该类化合物的后续研究提供参考。

关键词脱氢枞胺;衍生物;先导化合物;生物活性;研究进展

中图分类号:R914.5    文献标识码:A       文章编号:0258-32832022--

 

Research Progress of Biological Activities for Dehydroabietylamine Derivatives HUANG Jing-ling, LIANG Jin-ping, ZHOU Feng-ji, HE Jin-zhi, ZHANG Zhen-wei, 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, 2022, 44(11),

Abstract: Dehydroabietylamine is one of the important modification substances of rosin, and also the main component of disproportionated rosin amine. It has a stable chiral tricyclic phenanthrene structure and modifiable amine group, which can be recognized with biological macromolecules. It is an important medicinal skeleton. Its derivatives have antibacterial, antiviral, and anticancer activities and can be used as lead compounds for new drug discovery. The biological activities of dehydroabietylamine derivatives were classified according to their different biological activities, and the research progress on the biological activities of dehydroabietylamine derivatives was introduced in order to provide a reference for the subsequent research of dehydroabietylamine derivatives.

Key words: dehydroabietylamine; derivative; lead compound; biological activity; research progress

引用本文:黄静玲,梁锦萍,周凤姬,等. 具有生物活性的脱氢枞胺衍生物研究进展[J]. 化学试剂,2022,44(11): 1585-1597.

 

 

FMNH介导偶氮苯还原机理的密度泛函理论研究

 

宋佳宸,郑大威,王圣博,王娇娇,孙国辉,张娜,赵丽娇*,钟儒刚

(北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室,北京  100124

 

摘要:实体瘤的低氧微环境是恶性肿瘤的重要特征之一,针对肿瘤低氧的靶向化疗药物为癌症治疗带来了新策略。偶氮苯中的偶氮基团具有低氧激活的特异性,能够在常氧条件下稳定存在而在低氧条件下发生还原裂解,因此一些偶氮苯衍生物前药也因其具有肿瘤低氧靶向潜力近年来被开发并应用于临床研究。使用密度泛函(DFT)方法对在辅酶还原型黄素单核苷酸(FMNH)作用下的偶氮苯还原机理进行了研究。结果表明,优势反应路径为偶氮苯首先经过连续的两步1e-/1H+转移形成1,2-二苯肼,然后依次再发生第31e-/1H+转移、氮氮裂解和第41e-/1H+转移后最终形成两分子苯胺;其中,前两步1e-/1H+转移需要克服最高能垒,为反应的控速步骤。这些结果为设计开发新型的肿瘤靶向性低氧激活前药提供了重要理论依据。

关键词偶氮苯;低氧激活前药;还原机理;密度泛函理论;肿瘤低氧

中图分类号:O641    文献标识码:A       文章编号:0258-32832022

 

Reduction Mechanism of Azobenzene Mediated by FMNH: A DFT Investigation SONG Jia-chen, ZHENG Da-wei, WANG Sheng-bo, WANG Jiao-jiao, SUN Guo-hui, ZHANG Na, ZHAO Li-jiao*, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment & Life, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2022,

Abstract: The hypoxic microenvironment of solid tumor a significant feature of malignant tumor, so that the hypoxia-targeted chemotherapies have become a new strategy for the treatment of cancer. The azo groups in azobenzene have the specificity of hypoxia activation, which can be stable under normoxic condition while be activated under hypoxic condition. Therefore, some azobenzene derivative prodrugs have been developed and applied to clinical research in recent years because of their tumor-hypoxia targeting potential. In this study, the reduction mechanism of azobenzene mediated by the coenzyme reduced flavin mononucleotide (FMNH) was studied by density functional theory (DFT). The results indicated that the dominant pathway of the reduction was that azobenzene underwent successive two steps of 1e-/1H+ transfer to yield 1,2-diphenylhydrazine, followed by the formation of two aniline molecules via the third 1e-/1H+ transfer, cleavage of azo groups and then the forth 1e-/1H+ transfer. The rate-determining step was the first two steps of 1e-/1H+ transfer, which needed to overcome the highest energy barriers. This study provides an important theoretical basis for the design and development of novel hypoxia-activated prodrugs with tumor targeting.

Key wordsazobenzene; hypoxia-activated prodrug; reduction mechanism; density functional theory; tumor hypoxia

引用本文:宋佳宸, 郑大威, 王圣博, . FMNH介导偶氮苯还原机理的密度泛函理论研究[J]. 化学试剂, 2022, 44(11):1598-1604.

 

 

胡椒酸己二醇单酯的降血脂作用及其与牛血清白蛋白相互作用研究

宝贵荣1,金亮2,包仓1,博·格日勒图3,领小*3

 

1. 呼和浩特民族学院 化学与环境学院,内蒙古 呼和浩特  010051

2. 内蒙古自治区国际蒙医医院国家新药临床试验机构,内蒙古 呼和浩特  0100653. 内蒙古大学 化学化工学院 蒙药化学重点实验室,内蒙古 呼和浩特  010021

 

摘要:以胡椒碱为起始原料,经水解和酯化反应合成了胡椒酸己二醇单酯,纯度为99.43%,总产率为36.21%其化学结构经IR1HNMR13CNMRUV和元素分析予以表征。同时建立Wistar大白鼠高脂模型评价降血脂活性,并采用紫外分光光度法和荧光光谱法研究胡椒酸己二醇单酯与牛血清白蛋白(BSA)相互作用。研究结果表明,胡椒酸己二醇单酯显著降低Wistar大白鼠血清中的总胆固醇水平,显著升高了高密度脂蛋白胆固醇水平,降低了甘油三酯和低密度脂蛋白胆固醇水平;在模拟生理条件下(pH 7.40),胡椒酸己二醇单酯与牛血清白蛋白形成内源性荧光猝灭,主要为静态猝灭;猝灭常数随温度升高而降低,结合位点数n分别为1.36 (25 ℃)1.33 (37 ℃);通过热力学参数分析,胡椒酸己二醇单酯与牛血清白蛋白的相互作用是吉布斯自由能降低和熵增加的自发过程,主要是疏水作用力。

关键词:胡椒碱;降血脂;牛血清白蛋白;荧光光谱

中图分类号: O657                文献标识码:          文章编号:

 

Study on the Anti-hyperlipidemic Activity of 1.6-Hexanediol Piperinic-monoester and Its Interaction with Bovine Serum Albumin  BAO Gui-rong1, JIN Liang2, BAO Cang1, BORIJIHAN Gereltu3, LING xiao3* 1.Department of Chemistry and Environment, Hohhot Minzu College, Hohhot, 010051, China; 2.State Clinical Trial Institution of New Drugs, International Mongolian hospital of Inner Mongolia, Hohhot 010065, China; 3.Institute of Mongolian Medicine Chemistry, school of chemistry and chemical Engineering, Inner Mongolia University, Hohhot 010021, China

Abstract: Using piperine as the starting material, the unreported hexanediol monoester of piperine was synthesized by hydrolysis and esterification, with a purity of 99.43% and a total yield of 36.2%. Its chemical structure was characterized by IR, 1HNMR, 13CNMR, UV and elemental analysis. At the same time, a Wistar rat hyperlipidemia model was established to evaluate the antihyperlipidemic activity, and the binding effect of the compound to bovine serum albuminBSAwas further studied by fluorescence spectroscopy and ultraviolet spectroscopy. The experimental results showed that the compound significantly reduced the level of TC in the serum of high-fat model Wistar rats, significantly increased the level of HDL-C, and decreased the levels of TG and LDL-C. Under the simulated physiological conditions of pH 7.40, the compound formed endogenous fluorescence quenching with BSA, and the main type was static quenching; the quenching constant decreased with the increase of temperature, and the number of binding sites n was 1.36 (25) and 1.33 (37), respectively. Through thermodynamic parameter analysis, the interaction between the compound and BSA was found to be a spontaneous process of Gibbs free energy decrease and entropy increase, and the main force was hydrophobic force.

Key words: Piper Longum L; anti-hyperlipidemia; bovine serum albumin; fluorescence spectroscopy

引用本文:宝贵荣,金亮,包仓,等. 胡椒酸己二醇单酯的降血脂作用及其与牛血清白蛋白相互作用研究[J]. 化学试剂,202244(11): 1605-1609.

 

 

 

 

【功能材料】

化学气相沉积SiO2改性阻燃聚氨酯泡沫的制备及其性能

郑大为1a,朱英明*1b吴可荆1b,刘颖颖1b,唐思扬1a,刘胜强2付鹏程2鲁厚芳1a,1b梁斌1a,1b

(1.四川大学 a化学工程学院,b.新能源与低碳技术研究院,四川 成都  6100652.中储粮成都储藏研究院有限公司,四川 成都  610091)

 

摘要有机保温材料广泛应用于建筑节能,但由于有机保温材料存在很大的火灾隐患,而传统方法在提高阻燃性能的同时会牺牲有机保温材料的保温性能或力学性能。因此,提高其火灾安全性能的同时保留其优异的隔热性能是亟需解决的首要问题。报道了一种利用脉冲化学气相沉积方法在聚氨酯泡沫表面沉积SiO2阻燃层的方法,在气相氛围中低温沉积实现表面功能化,避免了对聚氨酯泡沫的结构破坏。通过极限氧指数仪、垂直燃烧仪等分析改性后聚氨酯的阻燃抑烟性能,极限氧指数达到了29.7%,通过了垂直燃烧V-0等级测试。导热系数测试结果为30.3 mW/(m·K)。对阻燃机理分析结果表明,SiO2促进了表面成炭阻燃过程,形成了更稳定有效的阻燃炭层结构。

关键词:化学气相沉积(CVD);表面阻燃技术;聚氨酯泡沫;二氧化硅(SiO2

中图分类号:TQ328.3        文献标识码:A          文章编号:0258-32832022--

 

Preparation and Properties of SiO2 Modified Flame-retardant Polyurethane Foams by Chemical Vapor Deposition ZHENG Da-wei1a, ZHU Ying-ming*1b, WU Ke-jing1b, LIU Ying-ying1b, TANG Si-yang1a, LIU Sheng-qiang2, FU Peng-cheng2, LU Hou-fang1a,1b, LIANG Bin1a,1b (1. Low-Carbon Technology and Chemical Reaction Engineering Laboratory, School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China; 2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu, 610065, P. R. China; 3. Sinograin Chengdu Storage Research Institute Co. Ltd, Building 32, No.239 Guangfu Road, Qingyang District, Chengdu P. R. China), Huaxue Shiji, 2022, 44(11),

Abstract: Thermal insulation materials, especially polymeric materials, have been widely used in buildings to reduce energy consumption, but raditional polymeric thermal insulation materials are easily ignited. However, traditional methods will sacrifice the thermal insulation properties or mechanical properties of polymeric thermal-insulation materials while improving the flame retardant properties. Therefore, it is an urgent task to improve its fire safety performance while retaining its excellent heat insulation performance. In this work, we report an efficient and mild strategy of pulsed chemical vapor deposition (Pulsed-CVD) to generate the SiO2 nano layer on the rigid polyurethane foams to achieve flame-retardancy. The SiO2/PUF showed closed-cell structure with extra-ordinary thermal conductivity of 30.3 mW/(m·K) and the value of limited oxygen index (LOI) substantially increased to 29.7% with silica nano layers. The mechanism of the enhanced flame retardancy highly related to the formation of stable chars by SiO2 nano layers.

Key wordschemical vapor deposition (CVD); surface flame-retardant treatment; polyurethane foam (PUF); SiO2

引用本文:郑大为,朱英明,吴可荆,等. 化学气相沉积SiO2改性阻燃聚氨酯泡沫的制备及其性能[J]. 化学试剂,2022,44(11): 1610-1618.

 

COF/CdS复合材料的制备及其可见光催化性能研究

 

韦云娇,韦欣仪,韦春雨,杨杰艺,覃仙红,袁香米,陆俊宇*

(河池学院 化学与生物工程学院,广西 宜州  546300

 

摘要:为开发可见光响应型共价有机框架(COFs)材料,以COFs材料为基底构筑异质结催化剂,达到高效利用太阳能进行催化降解有机染物。首先以三醛基间苯三酚和2,5-二氨基-1,4-苯二硫酚为构筑单体,制备一种巯基功能化COFsHS-COF)作为基底材料,并利用巯基锚定Cd2+,然后以硫脲为硫源,通过原位生长法,实现在基底HS-COF表面原位生长CdS纳米颗粒,并利用透射电子显微镜、傅里叶红外光谱、X-射线衍射以及X-射线光电子能谱对所制备的复合材料(COF/CdS表面的微观形貌进行表征。实验以罗丹明BRhB为模型污染物在可见光照射条件下考察COF/CdS复合材料的光催化降解性能。结果表明,CdS纳米成功固载在基底COF材料表面,其对RhB降解率高达92.5%反应速率常数为0.0145 min-1单相COF材料CdS纳米颗粒及物理混合COF/CdS相比,其表现出更强的可见光催化性能,这表明COF/CdS具有优异的光催化活性。此外,该异质结催化剂具有良好的稳定性,经5次循环使用后对RhB降解率仍在75%以上

关键词共价有机框架;硫化镉;光催化;降解;罗丹明B

中图分类号:TB33O643.3    文献标识码:A       文章编号:0258-32832022

 

Preparation and Visible Light Photocatalystic Property of COF/CdS Composites  WEI Yun-jiao, WEI Xin-yi, WEI Chun-yu, YANG Jie-yi, QIN Xian-hong, YUAN Xiang-mi, LU Jun-yu* (College of Chemistry and Biology Engineering, Hechi University, Yizhou 546300, China), Huaxue Shiji, 2022,

Abstract: In order to develop visible light-responsive covalent organic frameworks (COFs) materials, heterojunction catalysts were constructed based on COFs materials to make efficient use of solar energy for photocatalytic degradation of organic dyes. First, trialdehyde phloroglucinol and 2,5-dimercapto-1,4-phenylenediamine as the building monomers, a thiol-modified COFs (HS-COF) is prepared as a substrate material, and Cd2+ is anchored by thiol group, then thiourea is used as the sulfur source, CdS nanoparticles were grown on the surface of COFs by in-situ growth method and various techniques, including transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy were applied to evaluate the morphological features of the as-obtained photocatalysts. Under visible light irradiation, the photocatalytic degradation performance of COF/CdS composites was investigated by degradation of rhodamine B (RhB as model pollutant). The experiment results proved that CdS nanoparticles were successfully immobilized on the surface of COF substrate, and the photodegradation efficiency of COF/CdS composites was up to 92.5%, and the reaction rate constant was 0.0145 min-1. Compared with pure COF materials, CdS nanoparticles and physical mixed COF/CdS, the prepared COF/CdS composites showed much higher photocatalytic performance. Besides, after the COF@CdS composites have been reused five times,the degradation efficiency was still over 75%, this result indicated that the as-prepared heterojunction catalyst has excellent stability.

Key wordscovalent organic frameworks; CdS; photocatalytic; degradation; Rhodamine B

引用本文:韦云娇, 韦欣仪, 韦春雨, . COF/CdS复合材料的制备及其可见光催化性能研究[J]. 化学试剂, 2022, 44111619-1626.

 

 

【电化学和新能源】

Ni-K /SiO2催化剂逆水煤气变换反应性能研究

鲁新康,杨继亮,韩翠,公丹丹,王路辉*

浙江海洋大学 石油化工与环境学院,浙江 舟山  316022

 

摘要:逆水煤气变换反应能够将CO2加氢转化为更有价值的CO,被认为是最有大规模应用前景的二氧化碳转化途径之一。通过浸渍法制备了不同K含量的5%Ni-K/SiO2催化剂,研究了K助剂对催化剂逆水煤气变换反应性能的影响。研究结果表明,5%Ni/SiO2催化剂中添加金属K作为助剂,能够有效地抑制反应过程中副产物CH4的产生,并且K含量为3 wt%时,催化剂有着最好的催化性能。5%Ni-3%K/SiO2催化剂在600 ℃的高温中反应无CH4产生且反应10 h性能稳定。催化剂表征结果表明,加入K助剂减弱了催化剂对CO的吸附强度,使得CO更容易从催化剂表面脱附,进而阻碍了CO进一步加氢生成CH4。同时K助剂能够增强载体与NiO之间的相互作用,提高了催化剂的稳定性。

关键词:逆水煤气变换反应;催化剂;K助剂;选择性

中图分类号:X701.3           文献标识码:A       文章编号:

 

Study of the Catalytic Performance of Ni-K/SiO2 Catalyst for Reverse Water-gas Shift Reaction LU Xin-kang, YANG Ji-liang, HAN Cui, GONG Dan-dan, WANG Lu-hui* (College of Petrochemical and Environment, Zhejiang Ocean University, Zhoushan  316022, China) , Huaxue Shiji202244 (11 )

AbstractReverse water gas conversion reaction can hydrogenate CO2 into more valuable CO, which is considered to be one of the most promising methods for large-scale application of CO2 conversion. In this study, we prepared 5%Ni-K/SiO2 catalysts with different K contents by impregnation method and investigated the promotion effect of K additives on catalysts in the reverse water-gas shift reaction. The results showed that the addition of metal K to the 5%Ni/SiO2 catalyst could effectively inhibit the production of CH4 during the reaction, and the catalyst with K content of 3 wt% had the best catalytic performance, and 5%Ni-3%K/SiO2 catalyst did not produce CH4 at 600 °C and not deactivate for 10 h. The reason was that the addition of K additive reduced the production of CH4 during the reaction. The catalyst characterization results showed that the addition of K weakens the adsorption strength of CO, which makes it easier to desorb CO from the catalyst surface and thus prevents further hydrogenation of CO to CH4, while the addition of K enhances the interaction between the support and Ni and improves the stability of the catalyst.

Key words: reverse water-gas shift; catalyst; K additive; selectivity

引用本文:鲁新康,杨继亮,韩翠,等. Ni-K /SiO2催化剂逆水煤气变换反应性能研究[J]. 化学试剂, 2022, 44( 11): 1627-1633

 

 

【化学品与环境】

磁性壳聚糖微球在有机废水处置领域的应用研究

 

朱明新*张进雨潘顺龙刘家扬周华

(南京工业大学 环境科学与工程学院,江苏 南京  211816

 

摘要:随着工业化的发展,社会的进步,我们人类无可避免的产生各种有机废水。如何高效处置工业有机废水成为业界亟待解决的关键问题。以磁性壳聚糖微球为代表的吸附回收技术由于其吸附效率高、绿色环保、可回收利用等优点备受业界关注。基于此,系统综述了近年来磁性壳聚糖微球吸附剂国内外相关研究进展,并对其未来发展趋势进行梳理和展望。该研究为磁性壳聚糖微球吸附剂在有机废水特别是工业有机废水处置领域的相关研究提供一定的理论基础。

关键词:磁性;壳聚糖;微球;吸附;有机废水

中图分类号:X703       文献标识码:A            文章编号:0258-32832022

 

Application Research of Magnetic Chitosan Microspheres in the Field of Organic Wastewater Disposal  ZHU Ming-xin*, ZHANG Jin-yu, PAN Shun-long, LIU Jia-yang, ZHOU Hua (School of Environmental Science and Engineering, Nanjing Tech University, Nanjing, 211816, China), Huaxue Shiji, 2022,

Abstract: With the development of industrialization and social progress, various organic wastewater is inevitably generated. How to efficiently dispose industrial organic wastewater has become a key issue to be solved urgently. Magnetic chitosan microspheres, as the representative of the adsorption-recovery technology has attracted much attention in the industry because of its high adsorption efficiency, green environment protection and recyclability. Herin, this work systematically reviews the relevant research progress of magnetic chitosan microsphere adsorbents at home and abroad in recent years, summarizes and prospects the future trend of magnetic chitosan microsphere adsorbents. It provides a certain theoretical basis for the research related to magnetic chitosan microsphere adsorbent in organic wastewater disposal, especially in the field of industrial organic wastewater.

Key words: magnetic; chitosan; microsphere; adsorption; organic wastewater

引用本文:朱明新, 张进雨, 潘顺龙, . 磁性壳聚糖微球在有机废水处置领域的应用研究[J]. 化学试剂, 2022, 44111634-1641.

 

 

Ti3C2Tx/Ti3AlC2复合相的制备及其对染料吸附行为研究

王凯1李森2吕英*1

(1.西安石油大学 材料科学与工程学院,陕西 西安  7100652.中国石油长庆油田分公司 第十一采油厂,甘肃 庆阳  745000)

 

摘要:采用原位HF部分蚀刻MAXTi3AlC2)制备了层状MXene/MAX(Ti3C2Tx/Ti3AlC2)复合相,通过单因素分析法对3种染料亚甲基蓝(MB)、孔雀石绿(MG)和吖啶黄素(AF)进行吸附性能研究。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)、全自动比表面及孔隙度分析仪(BET)对样品物相、晶体结构、形貌和比表面积进行了表征,系统研究吸附剂投加量、染料初始浓度和溶液pHTi3C2Tx/Ti3AlC2复合相吸附MBMGAF3种染料的性能影响。结果表明:Ti3C2Tx/Ti3AlC2MBMGAF3种染料的最大去除效率分别为99.56%99.86%79.32%,最大吸附量分别为59.3595.7412.12 mg/g,均优于商用活性炭。同时,发现Ti3C2Tx/Ti3AlC2MBMG的吸附效果对pH没有依赖性,对AF的吸附行为在酸性条件下吸附效果更优。3种染料吸附等温模型均符合Freundlich模型,吸附动力学符合准二级动力学模型,吸附过程主要归因于Ti3C2Tx/Ti3AlC2复合相表面官能团参与的化学吸附以及静电作用共同控制

关键词:MXene;染料;吸附模型;动力学;吸附机理

中图分类号:TB34TQ9         文献标识码:A      文章编号:0258-32832022--

 

Preparation of Ti3C2Tx/Ti3AlC2 and its Adsorption Properties for Organic Dyes  WANG Kai1, LI Sen2, LV Ying*11. School of Material Science and Engineering, Xian Shiyou University, Xian 710065, China; 2. PetroChina Changqing Oilfield Branch, Eleventh Oil Production Plant, Qingyang 745000, China, Huaxue Shiji, 2022, ,

AbstractThe layered MXene/MAX (Ti3C2Tx/Ti3AlC2) composites were prepared by in situ HF partial etching of MAX (Ti3AlC2). The adsorption properties of methylene blue (MB), malachite green (MG) and acridine flavin (AF) were investigated by single-factor analysis method. The physical phase, crystal structure, morphology and specific surface area of the samples were characterized by XRD, FE-SEM and BET. The effects of adsorbent dosing, initial concentration of dyes and pH on the adsorption performance of Ti3C2Tx/Ti3AlC2 were systematically investigated. The results showed that the maximum removal efficiencies of Ti3C2Tx/Ti3AlC2 for MB, MG and AF dyes were 99.56%, 99.86% and 79.32%, respectively. The maximum adsorption capacities were 59.35, 95.74, and 12.12 mg/g, respectively, which were better than those of commercial activated carbon. Meanwhile, it was found that the adsorption effect of Ti3C2Tx/Ti3AlC2 on MB and MG was not dependent on pH, and the adsorption ability on AF was better under acidic conditions. The isothermal model for the adsorption of the three dyes were in accordance with the Freundlich model, and the adsorption kinetics were in accordance with the quasi-secondary kinetic model, which proved that the adsorption processes were mainly attributed to the joint control of chemisorption involving functional groups on the surface of Ti3C2Tx/Ti3AlC2 composite phase as well as electrostatic interactions.

Key words: MXene; dyes; adsorption model; kinetics; adsorption mechanisms

引用本文:王凯,李森,吕英. Ti3C2Tx/Ti3AlC2复合相的制备及其对染料吸附行为研究[J]. 化学试剂,202244111642-1649

 

 

【分析与测试】

大别山区金寨县杂交天麻和红天麻质量差异分析

 

巩晴晴1,2,俞年军*1,2,3,4,5,王广政1,2,邢丽花1,3,程鹤1,2,徐君1,2,杜方平6

1. 安徽中医药大学,安徽 合肥  230012

2. 安徽省中医药科学院 中药资源保护与开发研究所,安徽 合肥  230012

3. 安徽道地中药材品质提升协同创新中心,安徽 合肥  230012

4. 中药研究与开发安徽省重点实验室,安徽 合肥  230012

5. 新安医学教育部重点实验室,安徽 合肥  230012

6. 金寨县药用菌种植专业合作社,安徽 六安  237000

 

摘要:通过指纹图谱结合主成分综合评价分析大别山区金寨县天麻质量差异性。采用中药指纹图谱软件结合6个成分含量测定以及主成分综合评价对21批金寨天麻药材进行分析。建立金寨县天麻药材的指纹图谱,确定共有峰11个,相似度均大于0.9。在含量测定中,对羟基苯甲醇、巴利森苷B、巴利森苷C、巴利森苷A 4个成分在杂交天麻和红天麻中有显著性差异。综合评价函数显示其中排名位于前3名的天麻变型分别是S14杂交天麻、S9的杂交天麻、S20红天麻。研究发现大别山区金寨县杂交天麻和红天麻的质量具有一致性和差异性。

关键词:杂交天麻;红天麻;指纹图谱;主成分分析;差异性

中图分类号       文献标识码A         文章编号0258-32832022

 

Analysis on Quality Difference between Hybrid Gastrodia Elata and Gastrodia Elata F.elata in Jinzhai County of Dabie Mountains Region  GONG Qing-qing1,2, YU Nian-jun*1,2,3,4,5, WANG Guang-zheng1,2, XING Li-hua1,3, CHENG He1,2, XU Jun1,2, DU Fang-ping6,  Huaxue Shiji, 2022,

Abstract: To analyze the quality difference of Gastrodia elata in Jinzhai County, Dabie Mountains by Fingerprint and Principal Component Comprehensive Evaluation. The similarity evaluation system for chromatographic fingerprint of traditional Chinese medicine (2012 Edition) was used to analyze the similarity of 21 batches of Jinzhai Gastrodia elata. The contents of gastrodin, p-hydroxybenzyl alcohol, parishin E, parishin B, parishin C, and parishin A of Gastrodiae Rhizoma were determined and analyzed in combination with Principal Component Comprehensive Evaluation. The fingerprints of Gastrodia elata medicinal materials with 11 peaks in total and the similarity greater than 0.9 were established in Jinzhai. In the content determination, there are significant differences between the four components of p-hydroxybenzyl alcohol, parishin B, parishin C, and parishin A in Hybrid Gastrodia elata and Gastrodia elata f.elata. The comprehensive evaluation function shows that the top three varieties of Gastrodia elata are S14 Hybrid Gastrodia elata, S9 Hybrid Gastrodia elata and S20 Gastrodia elata f.elata. The quality of Hybrid Gastrodia elata and Red Gastrodia elata f.elata in Jinzhai County, Dabie Mountains is consistent and different.

Key words: hybrid Gastrodia elata; Gastrodia elata f.elata; fingerprint; principal component analysis; difference

引用本文:巩晴晴, 俞年军, 王广政, . 大别山区金寨县杂交天麻和红天麻质量差异分析[J]. 化学试剂, 2022,44111650-1656.

 

 

自动化解析气质联用数据分析不同产地沙枣花中的挥发性成分

 

吕毅1,张佳妮2,赵娟1,都青钰2,刘嘉楠2,张霞2,于永杰*2

1. 宁夏食品检测研究院(国家市场监管重点实验室(枸杞及葡萄酒质量安全)),宁夏 银川  7500022. 宁夏医科大学 药学院,宁夏 银川  750004

 

摘要将气质联用技术(Gas chromatography-mass spectrometryGC-MS)与自主开发的化学计量学数据处理软件autoGCMSDataAnal相结合,研究了我国西北地区沙枣花中的挥发性成分。采用同时蒸馏萃取技术提取样本中的挥发性成分,并利用气质联用仪采集化合物信息,将数据导入至autoGCMSDataAnal中自动进行色谱峰提取、共流出成分解析、化合物注册以及聚类分析。将筛选出的差异性成分导入NIST谱库鉴定出48个化合物(其中25个成分通过对照品予以验证),包括酯类、酸类、醛类、醇类、酚类、烯类等化合物,多数具有香味特征。主成分分析和层次聚类结果均显示不同地区的沙枣花样本能得到明显区分。不仅为不同产地沙枣花的精细化开发利用提供科学依据,所展示的技术也有望为植物样本中挥发性成分自动解析提供新的解决方案。

关键词:沙枣花;autoGCMSDataAnalGC-MS;同时蒸馏萃取;挥发性成分;化学计量学

中图分类号:O657.6    文献标识码:A       文章编号:0258-32832022

 

Analysis of Volatile Compounds in the Flowers of Elaeagnus Angustifolia L. by Automatic GC-MS Data Analysis Strategy LV Yi1, ZHANG Jia-ni2, ZHAO Juan1, DU Qing-yu2, LIU Jia-nan2, ZHANG Xia2, YU Yong-jie*2 (1. NingXia Food Testing and Research Institute (Key Laboratory of Quality and Safety of Wolfberry and Wine for State Administration for Market Regulation), Yinchuan 750002, China; 2. College of Pharmacy, Ningxia Medical University, Yinchuan 750004, China), Huaxue Shiji, 2022,

Abstractwe developed a strategy that combined gas chromatography-mass spectrometry with our developed chemometrics data processing software (autoGCMSDataAnal) to analyze Elaeagnus angustifolia L. flowers from the northwest China. The volatile components of all samples were extracted by using a simultaneous distillation extraction technique and compounds information was collected by GC-MS. The acquired data files were directly imported into autoGCMSDataAnal to automatically perform chromatographic peak extraction, coeluted component deconvolution, component registration, and sample clustering analysis. A total of 48 significant difference compounds were screened and identified by NIST spectrum library (25 compounds were verified by standards), including esters, acids, aldehydes, alcohols, and phenolics. Most of the compounds showed aroma characteristics. Results from both principal component analysis and hierarchical cluster analysis indicated that  Elaeagnus angustifolia L. flowers from different regions can be clearly separated. This study can not only provide scientific basis for the refined development and utilization of Elaeagnus angustifolia L. flowers, but also show a new solution for the automatic analysis of volatile compounds in plant samples.

Key wordsElaeagnus angustifolia L. flowers; autoGCMSDataAnal; GC-MS; simultaneous distillation extraction; volatile compounds; chemometrics

引用本文:吕毅, 张佳妮, 赵娟, . 自动化解析气质联用数据分析不同产地沙枣花中的挥发性成分[J]. 化学试剂, 2022, 44111657-1664.

 

 

右奈必洛尔中间体的手性光谱研究

杨蓓蓓,李莉*

中国医学科学院 北京协和医学院药物研究所,北京  100050

 

摘要1-[6--(2R)-3,4-二氢-2H-苯并吡喃-2-]-(1R)-1,2-乙二醇(INT是合成选择性β受体阻滞剂右奈必洛尔的关键中间体,其绝对构型决定了产物的立体化学特征。采用手性光谱学方法,对比其左旋异构体(-)-INT的实验电子圆二色谱(ECD)和(1R,2R)/(1S,2S)-INT的理论ECD图谱,以及解析金属试剂Mo2(OAc)4衍生化产生的诱导圆二色谱信号,确定(-)-INT异构体的绝对构型为(1R,2R)。同时,通过基于密度泛函理论的量化计算得到(1R,2R)/(1S,2S)-INT的比旋光度,建立了甲醇和氯仿中的比旋光度符号与该结构绝对构型的关联,为快速准确判断其立体结构提供了依据。

关键词:右奈必洛尔;电子圆二色谱;比旋光度;含时密度泛函理论;绝对构型

中图分类号:O641.6      文献标识码:A       文章编号:0258-32832022--

 

Chiroptical Study of the Key Intermediate of Dexnebivolol YANG Bei-bei, LI li* (Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing 100050, China), Huaxue Shiji, 2022, 44(11),

Abstract1-[(2R)-6-Fluorochroman-2-yl)]-(1R)-ethane-1,2-diol (INT) is a key intermediate in the synthesis route of dexnebivolol, which is a selective b-receptor blocker with antihypertensive activity. The absolute configuration of its levorotary isomer (-)-INT was established by multiple chiroptical methods, including comparison of experimental electronic circular dichroism (ECD) spectrum of (-)-INT and the calculated ECD of (1R,2R)/(1S,2S)-INT, and dimolybdenum tetraacetate [Mo2(OAc)4] method for chiral vic-diol moiety. Our results showed that (-)-INT should be 1R,2R configuration. Meanwhile, the specific optical rotation at the sodium D-line was calculated by using time-dependent density functional theory, to further correlate the relationship between the sign of optical rotation in methanol and chloroform and absolute configuration, which could facilitate the rapid and accurate discrimination of its stereostructure.

Key words: dexnebivolol; electronic circular dichroism; optical rotation; time-dependent density function theory; absolute configuration

引用本文:杨蓓蓓,李莉. 右奈必洛尔中间体的手性光谱研究[J]. 化学试剂,202244(11): 1665-1669.

 

 

新型低共熔溶剂液-液微萃取技术检测食品中的苏丹红类色素

袁琳,单志卓,桂旖淳,张毅*,王颖臻

(昆明学院 化学化工学院云南 昆明  650214)

 

摘要建立了一种基于绿色低共熔溶剂(DES)的漩涡辅助分散液-液微萃取(VA-DLLME)技术与高效液相色谱联用测定食品中苏丹红类色素的方法。结果表明,n(辛酸)∶n(己醇)=11时组成的低共熔溶剂对苏丹红具有最佳的萃取效率。对影响萃取效率的各种参数,包括低共熔溶剂的组成和用量、漩涡时间以及盐浓度等进行了优化。最佳萃取条件为:低共熔溶剂用量50 µL,漩涡时间4 min,盐浓度为1 mg/mL。在最优条件下,该方法线性关系良好,相关系数大于0.9983,检出限和定量限分别为1.01.5 ng/mL3.04.7 ng/mL。对番茄酱、甜辣酱、西瓜味芬达饮料在加标浓度下测定苏丹红,加标回收率为86.6%114.8%,相对标准偏差均小于9.8%,具有较好的重现性。因此该方法能简单、有效地应用于食品样品中苏丹红的检测。

关键词:低共熔溶剂;苏丹红类色素;漩涡辅助分散液-液微萃取;高效液相色谱(HPLC)

中图分类号:O656.3   文献标识码:A          文章编号:0258-32832022--

 

Deep Eutectic Solvent Assisted Liquid-liquid Microextraction of Susan Dyes from Food Samples YUAN Lin, SHAN Zhi-zhuo, GUI Yi-chun, ZHANG Yi*, WANG Ying-zhen (Department of Chemical Science & Technology, Kunming University, Kunming 650214, China), Huaxue Shiji, 2022, 44(11),

Abstract: A vortex-assisted dispersive liquid-liquid microextraction method together with high performance liquid chromatography was developed for the determination of Sudan dyes in food samples. The hydrophobic deep eutectic solvent, formed by caprylic acid and hexanol was used as the extraction solvent. The optimized conditions were as follows: amount of the eutectic solvent was 50 μL, vortex time was 4 min and the salt concentration was 1 mg/mL. The method exhibited good linearity with linear coefficients greater than 0.9983. Limits of detection and limits of quantification were in the range of 1.01.5 ng/mL and 3.04.7 ng/mL. Finally, the proposed method was successfully applied to the determination of three Sudan dyes in food samples (ketchup, sweet chili sauce and watermelon-flavored Fanta) with relative recoveries in the range of 86.6%114.8%, and the relative standard deviations (RSDs) were all lower than 9.8%. Therefore, the method can be simply and effectively applied to the detection of Sudan dyes in food samples.

Key words: deep eutectic solvent; sudan dyes; vortex-assisted liquid-liquid microextraction; high performance liquid chromatography (HPLC)

引用本文:袁林,单志卓,桂旖淳,等. 新型低共熔溶剂液-液微萃取技术检测食品中的苏丹红类色素[J]. 化学试剂, 2022, 44(11): 1670-1675.

【合成与工艺技术】

银催化的基于自由基加成的偶联反应研究进展

叶之未,林艾妮,郦勇,程凯*

(绍兴文理学院 浙江省精细化学品传统工艺替代技术研究重点实验室,浙江 绍兴  312000

 

摘要:近年来,银催化的偶联反应也已成为有机反应中一类新颖的重要合成策略,并广泛应用于各类碳-碳键和碳-杂键的构筑。银催化剂在氧化剂辅助下使底物生成自由基,经自由基加成历程实现条件温和、操作简单和可调控的选择性偶联反应。通过价廉稳定的银催化剂替代传统的过渡金属使得有机反应具有良好的选择性和官能团耐受性。从银催化的自由基加成型氟代反应、银催化的自由基加成型偶联反应构筑碳-杂键和银催化的自由基加成型偶联反应构筑碳-碳键三方面探讨了基于自由基加成型银催化偶联策略新反应的应用和进展。

关键词银催化;偶联反应;自由基加成;氟化反应;碳-/-杂键形成

中图分类号: O621.3       文献标识码:       文章编号: 2022.02492022

 

Research Progress on Silver-Catalyzed Coupling Reaction via Radical Addition YE Zhi-wei, LIN Ai-ni, LI Yong, CHENG Kai* (Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shaoxing University, Shaoxing 312000, China), Huaxue Shiji, 2022,

Abstract: Silver-catalyzed cross-coupling reactions have recently emerged as a new and important category of organic transformations that find versatile applications in the construction of carbon-carbon and carbon-heteroatom bonds in recent years. Silver-catalyzed selective coupling reaction of radical precursors are operational simplification under mild conditions and could be proceeded via controllable free-radical addition with the assistance of oxidants. The application of relatively cheap and stable silver catalysts to replace traditional transition metal catalysts enables the organic reactions to proceed with good selectivities and functional group tolerance. In the present review, we summarize various types of silver-catalyzed coupling strategies by radical addition, such as silver-catalyzed fluorination, silver-catalyzed coupling for carbon-hetero bond formation and silver-catalyzed coupling for carbon-carbon bond formation.

Key words: silver-catalyzed; coupling reaction; radical addition; fluorination reaction; carbon-carbon/carbon-hetero bond construction

引用本文:叶之未, 林艾妮, 郦勇, . 银催化的基于自由基加成的偶联反应研究进展[J]. 化学试剂, 2022, 44111676-1685.

 

 

稳定同位素标记苯丙氨酸-D5的合成研究

徐仲杰1,2,戴春华2,孙雯2,张鹏帅2,雷雯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:解决了新生儿苯丙酮尿症筛查所需关键内标试剂紧缺的现状,对稳定同位素标记苯丙氨酸的合成工艺进行研究。苯丙氨酸-D5的合成是以苯甲醛-D5为起始原料,经过还原、溴化得到溴化苄-D5,接着与二苯基亚甲基氨基乙腈反应制备得到苯丙氨酸-D5中间体,再经酸性条件下水解得到苯丙氨酸-D5。以投入的苯甲醛-D5的物质的量计算,苯丙氨酸-D5产率为67.1%。所合成的苯丙氨酸-D5产物经核磁共振波谱、高效液相色谱和质谱等表征确认,化学纯度99.0%,同位素丰度99.5 atom% D,可作为同位素内标用于新生儿苯丙酮尿症筛查。

关键词:稳定同位素标记;苯丙氨酸-D5;内标试剂;合成

中图分类号:TQ421.6            文献标识码:A           文章编号:0258-32832022--

 

Synthesis of Stable Isotope Labeled Phenylalanine-D5 XU Zhong-jie 1,2, DAI Chun-hua 2, SUN Wen2, ZHANG Peng-shuai2, LEI Wen2, 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, 2022, 44(11),

AbstractIn order to solve the shortage of the key internal standard reagent for neonatal phenylketonuria screening, the synthesis process of stable isotope labeled phenylalanine was studied. The synthesis of phenylalanine-D5 was taken benzaldehyde-D5 as starting material. Benzyl bromide-D5 was obtained by reduction and bromination, and then the intermediate of phenylalanine-D5 was prepared by reaction with diphenylmethylene amino-acetonitrile. At last, the phenylalanine-D5 was obtained by hydrolysis under acidic conditions. The yield of phenylalanine-D5 was 67.1% on the basis of the amount of benzaldehyde-D5. The synthesized phenylalanine-D5 product was characterized by NMR, HPLC and MS. Its chemical purity was 99.0% and isotope abundance was 99.5 atom % D. The prepared phenylalanine-D5 can be used as isotope internal standard reagent for screening newborn phenylketonuria.

Key wordsstable isotope labeling; phenylalanine-D5; internal standard reagent; synthesis

引用本文:徐仲杰,戴春华,孙雯,等. 稳定同位素标记苯丙氨酸-D5的合成研究[J]. 化学试剂,202244(11):1686-1689.

 

 

 

树豆酮酸B的全合成

 

殷智鑫1,2,许小婷1,2,郭兵3,汤磊2,王建塔1,2,范菊娣*1,2

1. 贵州医科大学 药学院,贵州 贵阳  550004

2. 贵州省化学合成药物研发利用工程技术研究中心,贵州 贵阳  550004

3. 贵州省常见慢性病发病机制和药物研究重点实验室,贵州 贵阳  550004

 

摘要:以4-甲氧基水杨酸甲酯为起始原料,经Williamson醚化、O[1,3]迁移和Claisen重排一锅反应、酚羟基甲基化保护、酯水解、C-H活化/环合级联反应、选择性脱甲基、水解6步反应合成树豆酮酸B,总收率为18.2%,化合物结构经1HNMR13CNMR ESI-HRMS表征,与目标产物相符。报道树豆酮酸B的全合成路线,为树豆酮酸B的开发应用奠定了基础。

关键词:树豆酮酸BC-H活化/环合级联反应;全合成

 

Total Synthesis of Cajanonic Acid B YIN Zhi-xin1,2, XU Xiao-ting1,2, GUO Bing3, TANG Lei2, WANG Jian-ta1,2, FAN Ju-di* (1. College of Pharmacy, Guizhou Medical University, Guiyang 550004; 2. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R&D, Guiyang 550004; 3. Guizhou Provincial Key Laboratory of Pathogenesis and Drug Research on Common Chronic Diseases, Guiyang 550004), Huaxue Shiji, 2022,

Abstract: Cajanonic acid B was synthesized from methyl 4-methoxysalicylate via one pot reaction of  Williamson etherification, O[1,3]-Migration and Claisen rearrangement, hydroxy protection, ester hydrolysis, C-H activation/annulation cascade reactions, selective demethylation, and hydrolysis with an overall yield of 18.2%. The chemical structure of synthesized compound was confirmed by 1HNMR, 13CNMR and ESI-HRMSconsistenting with the target product. The synthetic route of cajanonic acid B was reported, and laided a foundation for the development and application of cajanonic acid B.

Key words: cajanonic acid B; C-H activation/annulation cascade reactions; total synthesis

引用本文殷智鑫, 许小婷, 郭兵, . 树豆酮酸B的全合成[J]. 化学试剂, 2022, 44111690-1694.

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