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《化学试剂》2022年第4期中英文摘要(附整期文章PDF文档)

N-磷酰化氨基酸的研究进展和试剂化前景展望

罗建红,赵玉芬,倪锋*

(宁波大学 新药技术研究院,浙江 宁波  315211

 

摘要:磷是生命的重要元素之一,充分参与生命体的组成结构和各种生化反应。蛋白质磷酰化是迄今为止最常见的翻译后修饰。氨基酸是蛋白质的基本结构模块,其化学性质相对稳定。当氨基酸的氨基被磷酰化时,由于邻近羧基的参与,该氨基酸易被活化成为具有多种生化活性的微型活化酶。在酸性条件下,N-磷酰化氨基酸的高能P-N因为N原子容易质子化变得很不稳定,从而限制了N-磷酰化氨基酸的合成以及作为化学试剂的应用。因此,探索适合于各种N-磷酰化氨基酸的高效合成方法并掌控其化学活性具有潜在的应用价值。综述了N-磷酰化氨基酸的分类、合成方法以及化学性质等方面。同时,也讨论了该领域中亟待解决的问题,并对其前景进行了展望

关键词:磷;蛋白质磷酰化;氨基酸;N-磷酰化氨基酸;P-N

中图分类号: O627.51                  文献标码:A      文章编号0258-32832022

 

Research Progress and Reagent Prospect of N-Phosphorylated Amino Acids LUO Jian-hong, ZHAO Yu-fen, NI Feng* (Institute of New Drug Technology, Ningbo University, Ningbo 315211, China), Huaxue Shiji, 2022, 44(4)   

Abstract: Phosphorus is one of the important elements of life and is fully involved in the structural components and various biochemical reactions of life. Protein phosphorylation is by far the most common post-translational modification. Amino acids are the basic structural modules of proteins, and their chemical properties are relatively stable. When the amino group of the amino acid is phosphorylated, due to the participation of adjacent carboxyl groups, the amino acid can be easily activated to become a ' micro-enzyme ' with various biochemical activities. Under acidic condition s , the high-energy P-N bond of N-phosphorylated amino acids becomes unstable due to protonation of the N atom, which limits the synthesis of N-phosphorylated amino acids and their application as chemical reagents. Therefore, exploring an efficient synthesis method suitable for various N-phosphorylated amino acids and harnessing their chemical activity have potential value for their applications. In this review, the classification, synthetic methods and chemical properties of N-phosphorylated amino acids were summarized. At the same time, pending problems in this field are also discussed and the prospect is analyzed.

Key words: phosphorus; protein phosphorylation; amino acid; N-phosphorylated amino acids; P-N bond

引用本文:罗建红,赵玉芬,倪锋. N-磷酰化氨基酸的研究进展和试剂化前景展望[J]. 化学试剂2022, 44(4):485-494.

 

不同官能团改性壳聚糖吸附重金属的研究进展

 

刘义a,张淑琴*a,b任大军a,b,张晓晴a,b

(武汉科技大学a. 资源与环境工程学院;b. 冶金矿产资源高效利用与造块湖北省重点实验室,湖北 武汉  430081

 

摘要:壳聚糖作为一种储量丰富,未得到充分利用的有机聚合物,其在重金属吸附领域具有良好的应用前景。然而壳聚糖在酸性介质中易溶解、吸附选择性差、吸附容量低等缺点限制了其进一步应用。近年来研究人员通过对壳聚糖进行改性来改善其缺点已取得一些成果。鉴于此,综述了近几年关于壳聚糖改性的相关研究,重点归纳总结了利用胺基、羧基、巯基以及杂环等改性修饰制备壳聚糖吸附剂的研究,并用表格的方式对比分析了不同壳聚糖基吸附剂的应用效果和吸附机理。进一步展望了壳聚糖基吸附剂未来的发展方向,为开发高效的重金属离子吸附剂提供参考。 

关键词:壳聚糖;重金属;官能团;废水处理

中图分类号:X703      文献标志码:A      文章编号:0258-32832022

 

Research Progress on Adsorption of Heavy Metals by Modified Chitosan with Different Functional Groups LIU Yia, ZHANG Shu-qin*a,b, REN Da-juna,b, ZHANG Xiao-qinga,b (a. School of Resources and Environment Engineering; b. Hubei Provincial Key Laboratory for Efficient Utilization and Agglomeration of Metallurgical Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China), Huaxue Shiji, 2022, 44(4)

Abstract: As a kind of organic polymer with abundant reserves but without sufficient utilization, chitosan has a good application prospect in the field of heavy metal adsorption. However, the further application of chitosan is limited because of its high dissolvability in acidic medium, poor adsorption selectivity and low adsorption capacity. In recent years, researchers have made some achievements in modifying chitosan to improve its shortcomings. In view of this, the related research on chitosan modification in recent years was reviewed, and the research on preparation of chitosan adsorbents by modification of amine group, carboxyl group, sulfhydryl group and heterocyclic ring was summarized emphatically. The application effect and adsorption mechanism of different chitosan-based adsorbents were compared and analyzed in tables. The future direction of chitosan-based adsorbents is also prospected, which provides reference for the development of efficient heavy metal ion adsorbents.

Key words: chitosan; heavy metals; functional group; wastewater treatment

引用本文:刘义, 张淑琴, 任大军, .不同官能团改性壳聚糖吸附重金属的研究进展[J]. 化学试剂, 2022, 44(4): 495-503

 

 

基于光热治疗和光动力治疗的光学疗法用于肿瘤治疗

 

王刚1,2,3雷梦颖3周艳林1, 邹节明*1, 奉建芳*2,3

1. 桂林三金药业股份有限公司,广西 桂林5410042. 江西中医药大学 药学院,江西 南昌330004

3. 广西壮瑶药工程技术研究中心,广西 南宁530200

 

摘要:癌症已经成为威胁人类健康的头号杀手。尽管手术治疗、放化疗等手段成为临床治疗的主导,但是强侵入性以及不能忍受的毒副作用严重影响着患者的生活质量。因此,开发非侵入性、安全性高的光学治疗意义重大。目前,基于无机和有机材料的肿瘤光动力治疗(Photodynamic Therapy, PDT)和光热治疗(PhotothermalTherapy, PTT)研究取得了许多积极的成果。从光学治疗的作用机制、PTTPDT抗肿瘤的应用进行综述,会对更高效、更安全的光学治疗提供一定的理论指导。

关键词:光动力治疗;光热治疗;肿瘤;材料;联合应用

中图分类号R94       文献标识码A文章编号0258-32832022

 

PTT/PDT Based Phototheranostics for Tumor Therapy WANG Gang1,2,3, LEI Meng-Ying3, ZHOU Yan-lin1, ZOU Jie-ming*1, FENG Jian-fang*2,3(1. Guilin Sanjin Pharmaceutical Company Limited, Guilin 541004, China; 2. School of Phamacy, Jiangxi University of Chinese Medicine, Nanchang 330004, China; 3.Guangxi Zhuang Yao Medicine Center of Engineering and Technology, Nanning 530200, China), Huaxue Shiji, 2022, 44(4),

Abstract: Malignant tumor has become the leading reason of human’s death. Although surgical treatment, radiotherapy and chemotherapy are the dominant strategies in clinic, the highly invasive and intolerable toxic effects seriously affect patient’s quality of life. Therefore, it is of great significance to develop non-invasive and safe PTT/PDT based phototheranostics. Recently, many positive results have been achieved in PDT and PTT based on inorganic and organic materials. This paper will discuss the anti-tumor mechanism of phototheranostics, as well as the single and combined applications of PDT and PTT in tumor therapy. We hope that this review can inspire phototheranostics towards a more efficient and safer direction.

Key words: PDT; PTT; tumor; inorganic and organic materials; the combined application

引用本文:王刚,雷梦颖,周艳林,等. 基于光热治疗和光动治疗的光学疗法用于肿瘤治疗[J].化学试剂,2022444):504-513.

 

 

青蒿素及其衍生物的抗寄生虫活性研究进展

 

翟荣航,王合珍,王京,张磊*,徐应淑*

遵义医科大学 药学院 贵州省生物催化与手性药物合成重点实验室,贵州 遵义  563000

 

摘要青蒿素是一种从菊科蒿属植物黄花蒿(Artemisia annua L.)中分离出来的倍半萜类天然产物,具有广泛的生物活性,如抗肿瘤、抗炎、抗菌、抗恶性疟原虫等。青蒿素也是重要的抗疟先导化合物,目前临床上使用的青蒿素类抗疟药物有双氢青蒿素、蒿甲醚、青蒿琥酯。近年来的研究发现,青蒿素及其衍生物对弓形虫、血吸虫、犬型孢子虫、利什曼原虫等多种病原体也具有广泛的抑制活性。主要综述近年来青蒿素及其衍生物抗虫活性研究进展,期望对新型抗寄生虫类青蒿素药物的研发有所帮助

关键词青蒿素;结构修饰;衍生物;抗寄生虫;研究进展

中图分类号R284        文献标识码A      文章编号0258-32832022--

 

Progress in Antiparasitic Activities of Artemisinin and Its Derivatives ZHAI Rong-hang, WANG He-zhen, WANG Jing, ZHANG Lei*, XU Ying-shu* (Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, School of Pharmacy, Zunyi Medical University, Guizhou Zunyi 563000, China), Huaxue Shiji, 2022, 44(4),

Abstract: Artemisinin is one of natural sesquiterpenoids that extracted from Artemisia annua L., and it shows extensive biological activities, such as antitumor, anti-inflammatory, antibacterial and antiparasitic, etc.

Recent studies have shown that artemisinin and its derivatives have broad-spectrum inhibitory effects on pathogenic parasites, such as Toxoplasma gondii, Schistosoma japonicum, Neospora caninum and Leishmania, etc. This article reviews the progress of antiparasitic activities of artemisinin and its derivatives in recent years, which is expected to be helpful for the development of novel antiparasitic artemisinin drugs.

Key wordsartemisinin; structural modification; derivative; antiparasitic; research progress

引用本文翟荣航, 王合珍, 王京, .青蒿素及其衍生物的抗寄生虫活性研究进展[J]. 化学试剂,202244(4)514-521.

 

 

手性胆甾类荧光探针在食品检测中对中性分子的识别研究 

 

罗黎霞,马文珍,刘哲,叶英*,韩丽娟

(青海大学 农牧学院,青海 西宁  810016

 

摘要利用紫外分光光度滴定法、Job法、荧光滴定法研究考察了手性胆甾类荧光探针分子钳对有机酸、酚酸、含氮碱基的识别性能,并测定了主客体之间的结合常数和自由能变化值,建立了胆甾类荧光探针快速检测有机酸、酚酸、含氮碱基的方法。研究结果表明,主体分子钳与所考察丁香酸、香草酸、苹果酸、熊果酸、没食子酸、亚油酸、腺嘌呤、胞嘧啶均形成1:1型静态淬灭超分子配合物。并将该方法应用于香兰荚豆香草酸、小米糠油亚油酸、猪肝腺嘌呤的检测;检测结果表明,香兰荚豆中香草酸的含量为0.148 mg/g、小米糠油中亚油酸的含量为70 mg/g、猪肝中腺嘌呤的含量为81 mg/100g

关键词胆甾;分子识别;有机酸;酚酸;含氮碱基

中图分类号:063              文献标志码:A      文章编号:0258-32832022

 

Study on the Recognition of Neutral Molecules by Chiral Cholesteric Fluorescent Probes in Food Detection LUO Li-xia, MA Wen-zheng, LIU Zhe, YE Ying*, HAN Li-juan (College of Agriculture and Animal Husbandry, Qinghai University, Xining, 810016, China), Huaxue Shiji, 2022, 44(4)

Abstract: The recognition performance of chiral cholesteric fluorescent probe molecular toward organic acids, phenolic acids and nitrogenous bases was investigated using ultraviolet spectrophotometric titration, Job method, and fluorescence titration. The binding constant and free energy between host and guest was measured. A method for rapid detection of organic acids, phenolic acids and nitrogen-containing bases with cholesteric fluorescent probes was established. The research results show that the main molecular tweezers form 1:1 statically quenched supramolecular complexes with syringic acid, vanillic acid, malic acid, ursolic acid, gallic acid, linoleic acid, adenine, and cytosine. The method was applied to the detection of vanillic acid in vanilla pod, linoleic acid of millet bran oil, and adenine of pig liver. The results showed that the content of vanillic acid in vanilla pod bean was 0.148 mg/g, the content of linoleic acid in millet bran oil is 70 mg/g, and the content of adenine in pig liver is 81 mg/100g.

Key words: cholesterol; molecular recognition; organic acid; phenolic acid; nitrogenous base

引用本文:罗黎霞,马文珍,刘哲,等. 手性胆甾类荧光探针在食品检测中对中性分子的识别研究[J]. 化学试剂, 2022: 44(4), 522-530

 

 

型近红外氧杂蒽荧光染料用于线粒体荧光成像

曾红,郭小美朱玉莲,练萍,范小林,吴勇权*

(赣南师范大学 化学化工学院 江西省有机药物化学重点实验室,江西 赣州  341000

 

摘要:荧光成像具有操作简单、灵敏度高和实时等优点,而近红外荧光成像能够有效避免生物组织自发荧光干扰。通过设计和合成3个新型近红外氧杂蒽荧光染料NXD-1NXD-3用于细胞荧光成像。首先,3个氧杂蒽荧光染料分子结构得到核磁共振谱和高分辨质谱的确认。其次,详细研究了这些荧光染料的吸收光谱和荧光光谱,实验数据表明3荧光染料的发射光谱能够达到近红外区域,其中NXD-3的光谱更为红移,它的最大吸收和发光波长分别为611 nm759 nm。另外密度泛函理论(DFT)计算结果与实际测试光谱数据相匹配。最后,将制备的氧杂蒽荧光染料用于细胞荧光染色成像,实验结果表明荧光染料NXD-3具有良好的细胞线粒体靶向荧光标记效果。

关键词氧杂蒽近红外;线粒体;荧光染料荧光成像

中图分类号O625.15        文献标识码A          文章编号:0258-32832022

 

A Novel Near-infrared Xanthene Fluorescent Dye for Mitochondrial Fluorescence Imaging ZENG Hong, GUO Xiao-mei, ZHU Yu-lian, LIAN Ping, FAN Xiao-lin, WU Yong-quan* (Key Laboratory of Organo-pharmaceutical Chemistry, School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000, China), Huaxue Shiji, 2022, 44(4) 

Abstract: Fluorescence imaging has the advantages of simple operation, high sensitivity and real-time, while near-infrared fluorescence imaging can effectively avoid the interference of spontaneous fluorescence of biological tissues. In this work, three novel near-infrared xanthene fluorescent dyes NXD-1NXD-3 were designed and synthesized for cell fluorescence imaging. Firstly, the molecular structures of the xanthene fluorescent dyes were confirmed by 1HNMR and HR-MS. Secondly, the absorption and fluorescence spectra of these fluorescent dyes are studied in detail. The experimental data show that the emission spectra of the three fluorescent dyes can reach the near-infrared region, in which the spectrum of NXD-3 is more red-shifted, and its maximum absorption and emission wavelengths are 611 nm and 759 nm, respectively. In addition, the theoretical results obtained from density functional theory (DFT) calculations can match the measured spectral data for the three dyes. Finally, the prepared xanthene fluorescent dyes were used for cell fluorescence imaging. The experimental results show that the dye NXD-3 has a good effect of cell mitochondrial-targeted fluorescence labeling.

Key words: Xanthene; near-infrared; mitochondrial; fluorescent dye; fluorescence imaging

引用本文曾红,郭小美,朱玉莲, . 新型近红外氧杂蒽荧光染料用于线粒体荧光成像[J]. 化学试剂,202244(4): 531-537

 

 

基于四苯基乙烯-罗丹明的HClO/ClO-可视化荧光探针的合成及性质研究

张珍,陈佳敏,来素涵,曾竟*,李佳佳

新疆师范大学 化学化工学院,新疆 乌鲁木齐  830054

 

摘要:次氯酸(HOCl)/次氯酸盐(ClO-)作为一种强氧化剂应用广泛,在机体免疫防御中起着至关重要的作用,过量HOCl/ClO-对环境及人体造成潜在威胁因此,建立可靠、精准检测HOCl/ClO-的分析方法具有重要意义。通过缩合、还原两步合成得到具有聚集诱导性质的四苯基乙烯-罗丹明类衍化合物TPE-RhB2,探针TPE-RhB2在乙醇/水溶液中实现了对ClO-的可视化荧光识别,在505 nm处荧光发生猝灭,猝灭比为90.2%,同时在572 nm处出现一新的荧光发射峰。该探针在pH 1~12内荧光响应稳定,并具有较强的抗干扰能力和灵敏度,检出限低至5.32 × 10-7 mol/LStokes位移高达155 nm,有望在复杂环境中实现对ClO-的检测。通过ESI-MS谱初步确定ClO-通过氧化水解机制引起了荧光信号和探针溶液颜色变化,根据所建分析方法实现了实际水样中ClO-的检测

关键词:四苯乙烯;罗丹明B;聚集诱导发光;HClO/ClO-荧光探针

中图分类号:O621.2             文献标识码:A           文章编号:0258-32832022

 

Synthesis and Properties of HClO/ClO- Visual Fluorescent Probe Based on Tetraphenylethylene-Rhodamine ZHANG Zhen, CHEN Jia-min, LAI Su-han, ZENG Jing*, LI Jia-jiaCollege of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054, ChinaHuaxue Shiji, 2022

Abstract: Hypochlorous acid (HOCl)/ hypochlorite (ClO-) as a strong oxidant is widely used in life and plays a crucial role in the body's immune defense. Excessive HOCl/ClO- may pose a potential threat to the environment and human body. Therefore, it is of great significance to establish a reliable and accurate analysis method for HOCl/ClO- detection. In this paper, tetraphenylene-rhodamine derivatives TPE-RhB2 with aggregation induced fluorescence effect was synthesized by condensation and reduction. The probe TPE-RhB2 realized the visual fluorescence recognition of ClO- in ethanol/water. The color of the probe solution changed from light yellow to pink after adding ClO-, The fluorescence quenching occurred at 505 nm with a quenching ratio of 90.2%, and a new fluorescence emission peak appeared at 572 nm. The detection limit is as low as 5.32 × 10-7 mol/L, and the Stokes shift is as high as 155 nm. It is expected to realize the detection of ClO- in complex environment. The fluorescence signal and the color change of the probe solution caused by the oxidation hydrolysis mechanism of ClO- were preliminarily determined by ESI-MS spectrum, and the detection of ClO- in actual water samples was realized according to the established analytical method.

Key words: tetraphenylethylene; rhodamine B; aggregation induced luminescence; HClO/ClO- fluorescence probe

引用本文张珍,陈佳敏,来素涵,等. 基于四苯基乙烯-罗丹明的HClO/ClO-可视化荧光探针的合成及性质研究[J]. 化学试剂,202244(4):538-543

 

 

偶氮基双核钴配合物的合成、结构及光学性质

潘昊,陈琪骐,谢燕婷,梁晓彤,卢子豪,邱燕璇*

广东第二师范学院 化学与材料科学学院,广东 广州  510303

 

摘要室温下,通过调控反应体系的pH值,构筑了一例新的基于5-偶氮四唑水杨酸(H3ASA)的钴配合物[Co2(HASA)2(H2O)6] (1),并借助X-射线单晶衍射解析其晶体结构。结果显示,配合物1结晶于单斜晶系,P21/c空间群,每个不对称单元由两个Co(II)离子,两个HASA2-配体以及6个配位水分子组成。晶体结构中,中心离子Co(II)六配位八面体构型,配体HASA2-桥联两个不同的Co(II)离子形成双核结构,邻近的双核单元通过OH×××OOH×××NCH×××O 3种氢键相互作用形成3D超分子结构合物在室温下稳定,研究表明配合物在365 nm波长辐照展现出光致异构性质,在302 nm光激发下发出紫色荧光。

关键词偶氮化合物;晶体结构;钴;光致异构;荧光

中图分类号:O614    文献标识码:A       文章编号:0258-32832022

 

Synthesis, Structure and Optical Properties of a Azo-based Dinuclear Cobalt Complex PAN Hao, CHEN Qi-qi, XIE Yan-ting, LIANG Xiao-tong, LU Zi-hao, QIU Yan-xuan* (School of Chemistry and Materials Science, Guangdong University of Education, Guangzhou 510303, China), Huaxue Shiji, 2022, 44(4),

Abstract: A new Co(II) complex based on the 5-azotetrazolyl salicylic acid (H3ASA) ligand of [Co2(HASA)2(H2O)6] (1) was constructed via regulating the pH value of reaction system at room temperature and its crystal structure was characterized by single crystal X-ray diffraction. The result indicates that complex 1 forms dimer and crystallizes in the monoclinic space group P21/c with each asymmetric unit consisting of two Co(II) ions, two HASA2- ligands and six coordinated water molecules. In the crystal structure, the central ion Co(II) coordinates to six atoms, affording an octahedral geometry. Each HASA2- ligand acts as bridging ligand coordinating to two different Co(II) ions, resulting in a dinuclear structure. Three types of hydrogen-bonds of OH×××O, OH×××N and CH×××O connect the neighboring dinuclear structures into a 3D supramolecular framework. Complex 1 is stable at room temperature. The researches demonstrated that this complex displays photoisomerization property under 365 nm light radiation and purple fluorescence upon 302 nm light excitation.

Key words: azo compound; crystal structure; cobalt; photoisomerization; fluorescence

引用本文潘昊,陈琪骐,谢燕婷,等. 偶氮基双核钴配合物的合成、结构及光学性质[J]. 化学试剂,202144(4):544-549

 

 

三维网状化合物[(H2DABCO)CaCl4(H2O)2]的合成、结构及性能

 

胡宏志a刘洋*a,b刘颖a徐慧婷a刘尊奇*a,b

(新疆农业大学 a. 化学工程学院,b. 新疆农业化学生物材料重点实验室,新疆 乌鲁木齐  830052

 

摘要:1,4-二氮杂二环[2,2,2]辛烷(DABCO)、氯化钙、盐酸以一定比例溶入甲醇溶液,通过自然蒸发方式获得一种具有三维网状结构的新颖有机-无机杂化化合物[(H2DABCO)CaCl4(H2O)2],以红外光谱(IR)、元素分析、单晶X衍射、X-射线粉末衍射、热重分析(TG)、变温-变频介电等测试,确定化合物的结构及性能。结果显示化合物在低温(100 K)和室温(296 K)下空间群为P-1,属于三斜晶系,晶胞内[CaCl4(H2O)2]2-阴离子八面体结构发生变形,尤其是阴阳离子间的氢键相互作用改变导致所形成的三维网状结构发生明显的伸缩震动,致使化合物在ab轴方向上225 ~ 265 K温度范围内产生显著的介电异常现象。

关键词:1. 4-二氮杂二环[2,2,2]辛烷;氢键;三维网状结构;介电异常

中图分类号: O612.2             文献标识码:  A                    文章编号:0258-32832022

 

Synthesis, Structure and Properties of Three-Dimensional Network Compounds [(H2DABCO)CaCl4(H2O)2] HU Hong-zhia, LIU Yang*a,b, LIU Yinga, XU Hui-tinga, LIU Zun-qi*a,b (a. College of Chemical Engineering, b. Xinjiang Key Laboratory of Agricultural Chemistry and Biomaterials, Xinjiang Agricultural University, Urumqi, 830052, China), Huaxue Shiji, 2022, 44(4)

Abstract: A novel three-dimensional network structure of organic-inorganic compound [(H2DABCO)CaCl4(H2O)2], was synthesized through the natural evaporation method in the mixed solvent of methyl alcohol containing 1,4-diazabicyclo [2,2,2] octane (DABCO), calcium chloride and hydrochloric acid. The structure and properties of the compound were determined by infrared spectrum (IR), elemental analysis, single crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis (TG) and variable temperature-frequency dielectric test. The results show that the crystal all belongs to the triclinic crystal system of P-1 at low temperature (100 K) and room temperature (296 K). The octahedral structure of intracellular [CaCl4(H2O)2]2- anion is deformed. In particular, the change of hydrogen-bonding interaction between the cations and the anions leads to obvious stretching vibration of the forming three-dimensional network structure, resulting in the obvious dielectric anomaly of compound in the range of 225 ~ 265 K along the a and b axes.

Key words: 1,4-diazabicyclo [2,2,2] octane; hydrogen bond; three-dimensional network structure; dielectric anomaly

引用本文:胡宏志, 刘洋, 刘颖, 等.三维网状化合物[(H2DABCO)CaCl4(H2O)2]的合成、结构及性能[J].化学试剂, 2022, 444550-556.

 

 

超声波辅助双水相体系优化橘红花总黄酮提取工艺及其抗氧化活性

 

臧青民a,b,李秋珊a,徐燕波a,蒋德旗a,李海东a,章烨雯*a,b

玉林师范学院a. 生物与制药学院,b. 特色农林植物种质资源创新与应用研究中心,广西 玉林 537000

 

摘要:以总黄酮得率为响应值,采用响应面法优化超声波辅助双水相体系提取橘红花总黄酮工艺,并评估其抗氧化活性。在单因素实验基础上,选取乙醇浓度、硫酸铵浓度、超声温度为考察因素,采用Box-Behnken响应面分析法建立回归模型,筛选最佳提取工艺条件,并研究其清除DPPHABTS+自由基的能力。结果表明,超声波辅助双水相体系提取橘红花总黄酮的最佳条件为:乙醇浓度55%硫酸铵浓度为0.3 g/mL,超声温度50℃,超声时间30 min,液料比为20:1mL/g)。在此提取条件下,所得橘红花总黄酮得率为5.03%,与预测值较接近。抗氧化实验结果表明,橘红花总黄酮对DPPHABTS+自由基的IC50分别为0.1240.173mg/mL,与维生素C相比,抗氧化活性较弱。采用Box-Behnken响应面法优化的橘红花总黄酮提取工艺稳定可靠,可用于橘红花总黄酮的提取;橘红花总黄酮具有较强的抗氧化活性,为橘红花总黄酮的研究和开发利用提供了实验基础。

关键词:橘红花;总黄酮;响应面法;超声波;双水相提取;抗氧化活性

中图分类号R284.2       文献标识码:A      文章编号:0258-32832022--

 

Optimization of Ultrasonic-assisted Aqueous Two-Phase Extraction of Total Flavonoids from ExocarpiumCitriGrandisFlowers and its Antioxidant ActivityZANG Qing-mina,b, LI Qiu-shana, XU Yan-boa, JIANG De-qia, LI Hai-donga, ZHANG Ye-wen*a,b(a. College of Biology and Pharmacy; b. Research Center for innovation and application of characteristic agricultural and forestry plant germplasm resources, Yulin Normal University, Yulin, 537000, China), Huaxue Shiji, 2022, 44(4),

Abstract: Taking the yield of total flavonoids as response value, the ultrasonic-assisted aqueous two-phase method was used to optimize the extraction process of total flavonoids from exocarpiumcitrigrandisflowers, and its antioxidant activity was evaluated. Based on the single factor experiment, the regression model was established by Box-Behnken response surface analysis by selecting ethanol concentration, ammonium sulfate concentration and ultrasonic temperature as the investigation factors. The best extraction conditions were obtained, and the ability of scavenging DPPH and ABTS+ free radicals of the method was studied The results showed that the optimum extraction conditions for ultrasonic-assisted aqueous two-phase method of total flavonoids were as follows: ethanol concentration 55%, ammonium sulfate concentration 0.3 g/mL, ultrasonic temperature 50 ℃ultrasonic time 30 minsolvent-material ratios 20:1 (mL/g). Under this conditions, the yield of total flavonoids was 5.03%, which was close to the predicted value. The results of antioxidant experiments showed that the IC50 of the total flavonoids fromexocarpiumcitrigrandisflowers on DPPH and ABTS+ free radicals were 0.124 and 0.173mg/mL respectively, but weaker compared with vitamin C. The extraction process of total flavonoids from exocarpiumcitrigrandis flowers optimized by Box-Behnken response surface method is stable and reliable, and can be used for the extraction of total flavonoid fromexocarpiumcitrigrandis flowers.The total flavonoids from exocarpiumcitrigrandis flowers had strong antioxidant activity, and this study provides an experimental basis for the research, development and utilization of total flavonoids from exocarpiumcitrigrandis flowers.

Keywords: exocarpiumcitrigrandis flowers; total flavonoids; response surface methodology; ultrasonic; aqueous two-phase extraction; antioxidant activity

引用本文:臧青民,李秋珊,徐燕波,等.超声波辅助双水相体系优化橘红花总黄酮提取工艺及其抗氧化活性[J]. 化学试剂, 2022, 44(4):557-563

 

 

基于NO2的分离与富集光度法测定水中痕量NO2-

王春雨,李晓惠*,田亚赛,刘静璇,刘恩,许艳广

(辽宁科技学院 药化学院,辽宁 本溪  117004)

 

摘要在柠檬酸-乙醇介质中,NO2-被迅速转化成NO2利用吹气分离法将其转移至净化空气中;净化空气中的NO2与吸收液中的对氨基苯磺酸N-(1-萘基)乙二胺盐酸盐发生显色反应进而被富集,据此,水中痕量NO2-可采用分光光度法在540 nm波长处被间接测定。当采用三级吸收A= A1+A2+A3作为响应值,在拟定的实验条件下,NO2-转化系数83.5%,富集倍数10方法的测定线性范围3.066.7 μg/L之间。本方法有效消除了色度、浊度、盐分对NO2-测定的干扰检出限为0.9 μg/L,是国标法(GB 7493-87的十分之一,用于井水、溪水中NO2-的测定,RSD2.9%,回收率在96.6%102.2%之间,表明该方法适用于测定水中痕量NO2-

关键词NO2-;吹气分离;富集;分光光度法;测定

中图分类号: O65       文献标识码: A     文章编号:0258-32832022

 

Spectrophotometric Determination of Trace Nitrite in Water Based on the Separation and Enrichment of Nitrogen Dioxide WANG Chun-yu, LI Xiao-hui*, TIAN Ya-sai, LIU Jing-xuan, LIU En, XU Yan-guang ( Department of Biomedical and Chemical EngineeringLiaoning Institute of Science and TechnolgyBenxi 117004, China), Huaxue Shiji, 2022, 44(4)

Abstract: In citric acid-ethanol medium, NO2- was rapidly changed to NO2, which was transferred to purified air by air separation. The NO2 in purified air was enriched by undergoing color reaction with p-aminobenzene sulfonic acid and N-(1-naphthyl) ethylenediamine dihydrochloride in the absorption solution. Accordingly, the trace NO2- in water can be determined indirectly at 540 nm by spectrophotometric method. By using a three-stage absorption method with A= A1+A2+A3 as the response value, the obtained conversion coefficient of NO2- was 83.5% with the enrichment factor 10 and the linear range of determination 3.0 ~ 66.7 μg/L under the proposed experimental conditions. The interference of colority, turbidity and salinity to NO2- determination could be eliminated effectively with this method. The detection limit was 0.9 μg/ L, which was a tenth of that of the national standard method (GB 7493-87). The relative standard deviation was less than 2.9% and the recovery was between 96.6~102.2% when the method was applied to determine the trace NO2- in well water and river water, which indicated that the method was suitable for the determination of trace NO2- in water.

Key words: NO2-; air separation; enrichment; spectrophotometric method; determination

引用本文:王春雨,李晓惠,田亚赛,等. 基于NO2的分离与富集光度法测定水中痕量NO2[J]. 化学试剂,202244(4): 564-568

 

 

微波辅助制备巴旦木壳吸附剂对活性艳红X-B吸附性能研究

张建陈彦萍,李小敏*

(伊犁师范大学 化学与环境科学学院,污染物化学与环境治理重点实验室,新疆 伊宁 835000

 

摘要:以新疆厚皮原味巴旦木去仁所得壳作为原料进行实验,以0.7 mol/L的氯化锌活化制成活性炭。探索在各类波条件下,各种因素对巴旦木壳吸附活性艳红X-B的影响。微波协同巴旦木壳活性炭吸附剂对活性艳红X-B染料吸附有一定的效果,最佳吸附条件是0.5 g活性炭,100 mg/L活性艳红X-B染料,辐射时间2 min。吸附过程符合准二级动力学方程,是化学吸附。经过对比发现Langmuir吸附等温式拟合效果明显,是单分子层吸附。正交实验得出吸附量优化组合:t=1 minm=0.6 gc=300 mg/L。去除率组合:t=3 minm=0.6 gc=100 mg/L。极差分析得出,吸附量优化组合:t=2 minm=0.6 gc=300 mg/L。影响顺序:染料浓度大于吸附剂用量大于吸附时间。去除率的优化组合:t=3 minm=0.6 gc=300 mg/L。影响顺序:染料浓度大于吸附剂用量大于吸附时间。方差分析得出,吸附量的影响顺序:染料浓度影响最大,吸附剂用量次之,吸附时间影响最小。去除率的影响顺序为染料浓度最大,吸附剂用量次之,吸附时间对实验结果影响不大。

关键词巴旦木壳;活性炭;活性艳红X-B吸附性能;微波

中图分类号:TQX703.1      文献标识码:A      文章编号0258-32832022--

 

Study on the Adsorption Properties of Microwave-assistant Prepared Bayan Wood Shell Adsorbent on Active Bright Red X-B ZHANG Jian, CHEN Yan-ping, LI Xiao-min* (School of Chemistry and Environmental Sciences, Yili Normal University, Key Laboratory of Pollutant Chemistry and Environmental Governance, Yining 835000, China), Huaxue Shiji, 2022, 44(4)

AbstractActivated carbon was prepared from the shell of xinjiang thick-skinned original sinian as raw material and activated with 0.7 mol/L zinc chloride. We explored the effects of various factors on the adsorption activity of brilliant red X-B on sinian wood shells under different wave conditions. Microwave combined with activated carbon adsorbent of sinian wood shell has a certain effect on the adsorption of reactive brilliant red X-B dye. The optimal adsorption condition is 0.5 g activated carbon, 100 mg/L reactive brilliant red X-B dye, and the radiation time is 2 min. The adsorption process conforms to the quasi-second order kinetic equation and is chemical adsorption. By comparison, the Langmuir adsorption isothermal fitting method was found to be effective in monolayer adsorption.The optimal combination of adsorption capacity was obtained by orthogonal experiment: t=1min, m=0.6 g, and c=300 mg/L.Combination of removal rates: t=3 min, m=0.6 g, c=100 mg/L.Range analysis showed that the optimal combination of adsorption capacity was t=2 min, m=0.6 g, and c=300 mg/L.Influence order: dye concentration > adsorbent dosage > adsorption time. The optimal combination of removal rate:t=3 min, m=0.6 g, c=300 mg/L. Influence order: dye concentration > adsorbent dosage > adsorption time.Anova showed that the order of influence of adsorption amount was as follows: dye concentration had the greatest influence, followed by adsorbent dosage, and adsorption time had the least influence.The order of influence of removal rate: dye concentration is the largest, followed by the amount of adsorbent, adsorption time has little influence on the experimental results.

Key words: almond shell; activated carbon; reactive brilliant red X-B; adsorption property; microwave

引用本文:张建,陈彦萍,李小敏. 微波辅助制备巴旦木壳吸附剂对活性艳红X-B吸附性能研究[J].化学试剂,2022444):569-576.

 

 

不同氧化剂对土壤中有机氯农药γ-HCH降解效果的影响

 

项文霞*1,李义连2,李钊3,陈金国1

1. 湖北省地质局第三地质大队,湖北 黄冈4380002.中国地质大学(武汉) 环境学院,湖北 武汉430074

3. 黄州区自然资源和规划局,湖北 黄冈438000

 

摘要有机氯农药γ-HCH杀虫活性强,化学性质稳定,在环境中不易降解,残留期长,对生态环境和人体危害严重。通过加速溶剂萃取法联合气相色谱法,研究了Fenton试剂、热活化的Na2S2O8对土壤中有机氯农药γ-HCH的降解效果。结果表明,Fenton试剂和Na2S2O8在氧化降解γ-HCH方面都表现出很高的活性。当水土质量比为2.5 : 1,反应温度为25 oCFe2+H2O2投加量分别为0.2 mmol10 mmol时,γ-HCH去除率为88%;当水土质量比为2.5 : 1,反应温度为50 oCNa2S2O8投加量为5 mmol时,γ-HCH去除率为91.78%。使用Fenton试剂和Na2S2O8分别作为氧化剂对γ-HCH的去除均符合准一级反应动力学模型,其反应速率和去除率与水土比、反应温度、氧化剂投入量等因素有关。在优化后的反应条件下,使用Na2S2O8氧化降解γ-HCH的反应速率常数和反应半衰期分别为0.003 min-13.85 h;相较于Fenton试剂,其反应速率常数提高了约50%,反应半衰期缩短了约35%

关键词Fenton试剂;Na2S2O8γ-HCH;脱氯;氧化降解;反应动力学

中图分类号X53    文献标识码A      文章编号0258-32832022--

 

Effects of Different Oxidants on Degradation of Organochlorine Pesticide γ-HCH in Soil XIANG Wen-xia*1, LI Yi-lian2, LI Zhao3, CHEN Jin-guo1 (1. Third Geological Brigade of Hubei Geological Bureau, Huanggang 438000, China; 2. School of environmental studies, China University of Geosciences, Wuhan 430074, China; 3. Huangzhou Natural Resources and Planning Burea, Huanggang 438000, China), Huaxue Shiji, 2022, 44(4),

Abstract: Organochlorine pesticide γ-hexachlorocyclohexane (γ-HCH) has strong insecticidal activity and is difficult to be degraded in the environment due to its stable chemical properties and long residual period. γ-HCH is seriously harmful to the ecological environment and human. Through an accelerated solvent extraction coupled with gas chromatography method, the effect of Fenton reagent and thermally activated sodiumpersulfate on γ-HCH degradation in soil was studied. The results indicated that Fenton reagent and sodium persulfate displayed high reactivity to the oxidative degradation of γ-HCH When the amount of Fe2+ and H2O2 were 0.2 mmol and 10 mmol, respectively, the removal rate of γ-HCH was 88% at 25 oC and 2.5 g/g of water-soil ratio. When the dosage of sodiumpersulfate was 5 mmol, the removal rate of γ-HCH was 91.78% at 50 oC and 2.5 g/g of water-soil ratio. The degradation reaction of γ-HCH using Fenton reagent and sodiumpersulfate as oxidants conformed to a pseudo-first order kinetic model. The reaction rate and removal rate were affected by many factors, such as water-soil ratio, reaction temperature and the amount of oxidants. Under optimized reaction conditions, the reaction rate constant and reaction half-life time of γ-HCH degradation using sodium persulfate were 0.003 min-1 and 3.85 h, respectively. Compared with Fenton reagent, the reaction rate constant was increased by about 50%, and the reaction half-life time was shortened by about 35%.

Key words: Fenton reagent; sodium persulfate; γ-hexachlorocyclohexane; dechlorination; oxidative degradation; reaction kinetics

引用本文:项文霞, 李义连, 李钊, . 不同氧化剂对土壤中有机氯农药γ-HCH降解效果的影响[J].化学试剂,444577-583.

 

 

气相色谱质谱联用测定植物油中的非皂化物质

王建鑫,曹旭妮*

华东理工大学 食品科学与工程系,上海 200237

 

摘要:建立了测定植物油中的非皂化成分(角鲨烯及甾醇物质的气相色谱质谱联用分析方法,其检测限均小于2.00 mg/L,加标回收率为90.12%112.42%。采用该方法实现了山茶油、大豆油和玉米油的非皂化物质的含量分析。同时,通过分析还表明,山茶油中的豆甾醇大豆油或玉米油)中的存在显著差异β-谷甾醇大豆油与玉米油也存在显著差异,提示它们可能是防伪分析的重要参数所建立的方法具有高效、准确和灵敏的优点,这将为今后用于构建动态数据库用于综合评价植物油提供了一种分析方法。

关键词:气相色谱质谱联用法甾醇角鲨烯植物油

中图分类号O657.7    文献标识码A      文章编号0258-32832022--

 

Determination of Non-SaponifiableSubstances in Plant Oils by Gas Chromatography-Mass Spectrometry WANG Jian-xin, CAO Xu-ni* (Department of Food Science &Engineering, East China University of Science & Technology, Shanghai 200237, China), Huaxue Shiji, 2022, 44(4),

Abstract:This study established a method for the detection of the non-saponifiedsubstances(squalene and sterols) in plant oils by gas chromatography-mass spectrometry.The detection limits of the non-saponifiable substances were all lower than 2.00 mg/L and the recoveries were found to be 90.12%112.42%. This allowed to be used to analyze the contents of non-saponifiable substances in camellia oil, soybean oil and corn oil. Furthermore, the results showed that the stigmasterol in camellia oil was significantly different from that in soybean oil (or corn oil), and β-sitosterolwasalsosignificantly different between soybean oil and corn oil, suggesting that they may be an important parameter for anti-counterfeiting analysis. All together, these studies show that the established method has the advantages of high efficiency, accuracy and sensitivity, which provides an analytical method for constructing a dynamic database for comprehensive evaluation of vegetable oils in the future.

Key words:gas chromatography mass spectrometry; sterol; squalene; plant oil

引用本文:王建鑫,曹旭妮. 气相色谱质谱联用测定植物油中的非皂化物质[J]. 化学试剂, 2022, 44(4): 584-589

 

 

UHPLC快速测定豆浆粉中大豆异黄酮

李永利*,李杰,姜阳,吴建军,薛

上海市计量测试技术研究院 理化分析室 在线检测与控制技术重点实验室,上海  201203

 

摘要:为了同时测定豆浆粉中多种大豆异黄酮成分,建立了一种豆浆粉中大豆异黄酮的超高效液相色谱分析方法。样品由80%乙醇水溶液超声提取,经碱性条件皂化反应获得大豆异黄酮测试溶液。色谱柱采用Waters Atlantis T3,流动相为0.1%甲酸/水溶液-乙腈,梯度洗脱,流速为0.6 mL/minDAD检测器分析波长为260 nm。测定方法采用外标法定量,3个浓度下加标回收率为93.80% 97.99%,相对标准偏差(RSD<3.5%,检出限为0.4 0.5 mg/kg方法重现性好,适合豆浆粉基质中大豆异黄酮的快速测定。

关键词:大豆异黄酮;液相色谱;豆浆粉;含量测定

中图分类号: O657.7      文献标示码: A         文章编号0258-32832022

 

Determination of Soybean Isoflavones in Soymilk Powder by UHPLC LI Yong-li*, LI Jie, JIANG Yang, WU Jian-jun, Xue Min-jie (Physical and Chemical Analysis laboratory, Shanghai key Laboratory of Online Testing and Control Technology, Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China), Huaxue Shiji, 2022, 44(4)

AbstractA method was developed for simultaneous determination of soybean isoflavones in soymilk powder by ultra-high performance liquid chromatography (UHPLC). The analytes in soymilk powder were extracted by ultrasound extraction with 80% ethanol water solution, and the test solution was obtained by saponification reaction under alkaline conditions. Samples were separated over a Waters Atlantis T3 column. The mobile phase was composed of 0.1% formic acid aqueous solution and acetonitrile with flow rate of 0.6 mL/min, and DAD detection at 260 nm was applied. The recovery was 93.80%  97.99% at three levels,  the relative standard deviations (RSD) were less than 7.5%, and the limit of detection was 0.4 0.5 mg/kg. The method possesses good reproducibility, and is suitable for the determination of soybean isoflavones in soymilk powder. 

Key words: soybean isoflavone; liquid chromatography; soymilk powder; determination

引用本文李永利,李杰,姜阳,等.UHPLC快速测定豆浆粉中大豆异黄酮[J].化学试剂,2022444590-593.

 

 

超高效液相色谱串联质谱法测定中药保健品中6种有毒生物碱

许晓辉1王瑞1党子龙2,王小乔*1,张虹艳1,潘秀丽1,李晨曦1,李赟1

(1. 兰州市食品药品检验检测研究院,甘肃 兰州 7300502. 兰州大学第一医院药剂科,甘肃 兰州  730000

 

摘要建立了QuEChERS法净化,超高效液相色谱串联三重四极杆质谱UPLC-MS/MS测定中药类保健品中6种有毒生物碱含量的方法。样品以1%甲酸乙腈超声提取,BEH C18色谱柱(1.7 μm2.1 mm×100 mm)分离,以0.1%甲酸-2 mmol/L乙酸铵的水溶液与含0.1%甲酸的乙腈溶液为流动相梯度洗脱,三重四极杆质谱正离子多反应监测模式检测(MRM),外标法定量。在优化的色谱质谱条件下,6种生物碱在020 ng/mL线性关系良好,相关系数均大于0.9942。方法检出限(LODS/N=3)为0.0020.05 μg/kg,定量限(LOQS/N=10)为0.0070.15 μg/kg,在2510 μg/kg的加标浓度下,6种目标分析物的平均回收率范围为62.3%98.2%,相对标准偏差(RSD)为1.6%3.6%。该方法准确、高效、简便,适用于中药保健品中有毒生物碱的定性定量筛查。

关键词中药;保健品;超高效液相色谱串联质谱法;生物碱;有毒;测定

中图分类号R917      文献标识码A       文章编号:0258-32832022--

 

Determination of 6 Kinds of Toxic Alkaloids in Health Care Products from Traditional Chinese Medicine Using UPLC-MS/MS XU Xiao-hui1, WANG Rui1, DANG Zi-long2, WANG Xiao-qiao*1, ZAHNG Hong-yan1, PAN Xiu-li1, LI Chen-xi1, LI Yun1 (1. Lanzhou Institute for Food and Drug Control, Gansu Lanzhou 730050, China2. Department of Pharmacy, First Hospital of Lanzhou University, Gansu Lanzhou 730000, China), Huaxue Shiji, 2022, 44(4),

Abstract: A method was established for the determination of 6 toxic alkaloids in health care products from traditional Chinese medicine by QuEChERS method and ultra performance liquid chromatography-triple quadrupole tandem mass spectrometry (UPLC-MS/MS). The samples were extracted with 1% formic acid acetonitrile under ultrasonication, then separated on a BEH C18 column (1.7μm, 2.1mm×100 mm) by gradient elution, with 0.1% formic acid-2 mmol/L ammonium acetate of aqueous solution and acetonitrile solution containing 0.1% formic acid. The mass spectrometer was operated with positive ionization mode. The analytes were quantified by multiple-reaction monitoring (MRM) with external standards. . Under the optimized conditions of chromatography-mass spectrometry, the linear ranges for the six alkaloids were of 0-20 ng/mL, and the correlation coefficients were all greater than 0.9942, suggesting good linearity of the method. The limit of detection (LOD, S/N=3) and quantification (LOQ, S/N=10) of the method were 0.0020.05 μg/kg and 0.0070.15μg/kg, respectively. At three spiked levels (2, 5 and 10 μg/kg), the average recoveries for the target compounds were 62.3% to 98.2%, and the relative standard deviation (RSD) were 1.6% to 3.6%. The method was accurate, efficient, simple, and suitable for qualitative and quantitative screening of toxic alkaloids in health products from traditional Chinese medicine.

Key words: traditional Chinese medicine; health care products; ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS-MS) ; alkaloids; toxic; determination

 

引用本文:许晓辉,王瑞,党子龙,等. 超高效液相色谱串联质谱法测定中药类保健品中6种有毒生物碱[J]. 化学试剂,2022444594-598.

 

 

稳定同位素氘标记盐酸曲托喹酚的制备

秦爽1韩世磊1,2邵文哲1徐银1,2石静飞1,2佟庆龙1,2张磊*1,2

1. 天津阿尔塔科技有限公司,天津  3004572. 阿尔塔标准物质研究院,天津  300457

 

摘要:2-3,4,5-三甲氧基苯基)乙酸为起始原料,经过脱甲基、酰胺化、甲基化、比希勒-纳皮拉尔斯基(Bischler-Napieralski)环化反应、还原、脱保护基等关键反应步骤,得到稳定同位素氘标记的盐酸曲托喹酚。该合成方法原料廉价易得、简单成熟,目标产物氘同位素丰度较高。该产物经核磁共振氢谱(1HNMR)和高分辨质谱(HR-MS)表征确认,氘同位素丰度为99.9 atom%D,适合作为内标试剂用于曲托喹酚的定性定量分析。

关键词:稳定同位素标记;氘标记盐酸曲托喹酚;质谱内标试剂;同位素丰度

中图分类号:O628.1    文献标识码A      文章编号0258-32832022

 

Synthesis and Characterization of Stable Isotope Deuterium Labeled Tratoquinol Hydrochloride QIN Shuang1, HAN Shi-lei1,2, SHAO Wen-zhe1, XU Yin1,2, SHI Jing-fei1,2, TONG Qing-long1,2, ZHANG Lei*1,2 (1. Alta Scientific Co., Ltd., Tianjin 300457, China2. Alta Institute of Reference Materials Co., Ltd., Tianjin 300457, China), Huaxue Shiji, 2022, 44(4) 

Abstract: A novel deuterium-labelled tretoquinol hydrochloride was synthesized from 2-(3,4,5-trimethoxyphenyl) acetic acid via the steps of demethylation, amidation, alkylation, Bischler-Napieralski cyclization reaction, reductive, and deprotection. The synthetic route has the advantages of cheapaccessible starting materials and high isotope abundance. The deuterium-labelled product was confirmed by nuclear magnetic resonance (1HNMR) and high-resolution mass spectrometry (HR-MS) characterization with 99.9 atom% deuterium isotope abundance, which can be used as stable isotope-labeled MS internal standards for qualitative and quantitative analysis.

Key words: stable isotope labelling; deuterium labelled tretoquinol hydrochloride; MS internal standards; isotopic abundanceisotope abundance

引用本文秦爽,韩世磊,邵文哲,等. 稳定同位素氘标记盐酸曲托喹酚的制备[J]. 化学试剂,202244(4):599-603

 

 

标记克伦丙罗的合成方法研究与结构表征

曹炜东1,韩世磊1, 2,马秀婷1,徐银1, 2,石静飞1, 2,佟庆龙1, 2张磊*1, 2

1. 天津阿尔塔科技有限公司,天津  3004572. 阿尔塔标准物质研究院,天津  300457

 

摘要稳定同位素内标试剂与同位素稀释质谱法相结合的检测技术,为快速准确地检测β2-受体激动剂克伦丙罗的含量提供了可能。报道了一种新型的稳定同位素氘标记克伦丙罗的合成方法,以4-氨基-3,5-二氯-α-溴代苯乙酮为原料,经改良的Gabriel方法合成了伯胺化合物,再与丙酮-D6经还原胺化反应制备了稳定性同位素标记的克伦丙罗-D7,具有路线短、操作简便、总产率高等优点。该产物经核磁共振氢谱(1HNMR)和质谱(ESI-MS)表征确认,氘同位素丰度可达98.3 atom%可作为质谱内标试剂应用于兽残检测领域。

关键词:稳定同位素标记;克伦丙罗-D7;内标试剂;兽残检测

中图分类号:TQ463.7      文献标识码:A     文章编号:

 

Novel Synthesis Method and Characterization of Stable Isotope Deuterium Clenproperol CAO Wei-dong 1, HAN Shi-lei1,2, MA Xiu-ting1, XU Yin1,2, SHI Jing-fei1,2, TONG Qing-long1,2, ZHANG Lei*1,2 (1. Alta Scientific Co., Ltd., Tianjin 300457, China2. Alta Institute for Reference Materials Co., Ltd., Tianjin 300457, China), Huaxue Shiji, 2022, 44(4)

Abstract: Stable isotope internal standard reagent combined with isotope dilution mass spectrometry can offer a feasible method with accuracy and precision for the detection of β2-receptor agonist clenproperol. A novel synthetic method of stable isotope deuterium clenproperol. The primary amines were synthesized from 1-(4-amino-3,5-dichlorophenyl)-2-bromoethan-1-one by improved Gabriel method, and then the stable isotope labeled clenbuterol-D7 was prepared by reductive amination with acetone-D6. The novel synthesis route has the advantages of short route, easy operation, and higher yield. The deuterium-labeled product was confirmed by nuclear magnetic resonance (1HNMR) and mass spectrometry (ESI-MS) characterization with more than 98.3 atom% deuterium isotope abundance, which can be used as MS internal standards in the field of veterinary residues detection.  

Key words: stable isotope labeling; clenproperol-D7; MS internal standard reagent; veterinary residues

引用本文曹炜东,韩世磊,马秀婷,等. 氘标记克伦丙罗新的合成方法研究与结构表征[J]. 化学试剂, 2022, 44(4):604-607

 

 

盐酸莱克多巴胺-D6新的合成方法研究与结构表征

刘晓佳1,韩世磊1, 2,孔香玲1,徐银1, 2,石静飞1, 2,佟庆龙1, 2,张磊*1, 2

1. 天津阿尔塔科技有限公司,天津  3004572. 阿尔塔标准物质研究院,天津  300457

 

摘要:稳定同位素内标试剂与同位素稀释质谱法相结合的检测技术,为快速准确地检测莱克多巴胺的含量提供了可能。以4-(4-甲氧苯基)-2-丁酮为起始原料,经氢-氘交换、还原胺化、脱保护基反应,合成稳定同位素氘标记的盐酸莱克多巴胺。这条新的合成路线,具有路线短、操作简便、原料廉价易得等优点。合成产物经核磁共振氢谱(1HNMR)和质谱(ESI-MS)表征确认,氘同位素丰度97.7 atomD。可作为质谱内标试剂应用于兽残检测领域。

关键词:稳定同位素标记;氘标记莱克多巴胺;氢-氘交换反应;质谱内标试剂

中图分类号:O625.63    文献标识码:A     文章编号:0258-32832022

 

Novel Synthetic Method and Characterization of Ractopamine-D6 Hydrochloride LIU Xiao-jia1, HAN Shi-lei1,2, KONG Xiang-ling1, XU Yin1,2, SHI Jing-fei1,2, TONG Qing-long1,2, ZHANG Lei*1,2 (1. Alta Scientific Co., Ltd., Tianjin 300457, China2. Alta Institute for Reference Materials Co., Ltd., Tianjin 300457, China), Huaxue Shiji202244(4)

Abstract: Stable isotope internal standard reagent combined with isotope dilution mass spectrometry can offer a feasible method with accuracy and precision for the detection of ractopamine. A deuterium-labelled ractopamine hydrochloride was synthesized from 4-(4-methoxyphenyl) -2-butanone via the steps of H-D isotope exchange, reduction amination, and deprotection. The novel synthetic route has the advantages of short route, easy operation, cheap, accessible starting materials, and high isotope abundance and so on. The deuterium-labeled product was confirmed by nuclear magnetic resonance (1HNMR) and mass spectrometry (ESI-MS) characterization with more than 97 atom%D deuterium isotope abundance, which can be used as MS internal standards in the field of veterinary residues detection.

Key words: stable isotope labeling; deuterium-labeled ractopamine; H-D exchange reaction; MS internal standard reagent; veterinary residues detection

引用本文:刘晓佳,韩世磊,孔香玲,等. 盐酸莱克多巴胺-D6新的合成方法研究与结构表征[J].化学试剂,2022,44(4):608-612

 

 

4--6-甲氧基-7-[3-(4-吗啉基)氧基]喹啉的合成

 

赵培培,王刚,张帆*

(锦州医科大学 药学院,辽宁 锦州  121001

 

摘要4--6-甲氧基-7-[3-(4-吗啉基)氧基]喹啉是合成c-met激酶抑制剂Foretinib的重要中间体2-甲氧基-5-硝基苯酚为原料,在碳酸钾及碘化钾存在下与1--3-氯丙烷发生醚化反应,然后再与吗啉发生亲核取代反应,且将醚化及亲核取代两步反应合为一锅反应。再经铁粉还原、与米氏酸缩合、高温环合、氯代共6反应制得目标化合物反应总收率为32.4%。所有化合物结构经MS1HNMR进行确证。该路线步骤简洁耗时短操作简单,收率较高。

关键词4--6-甲氧基-7-[3-(4-吗啉基)氧基]喹啉;Foretinibc-met激酶抑制剂;抗肿瘤合成

中图分类号O625         文献标识码A          文章编号0258-32832022

 

Synthesis of 4-Chloro-6-methoxy-7-(3-(4-morpholine)propoxy)quinoline ZHAO Pei-pei, WANG Gang, ZHANG Fan*( College of Pharmacy ,Jinzhou Medical University, Jinzhou 121001, China), Huaxue Shiji, 2022, 44(4)

Abstract: 4-Chloro-6-methoxy-7-(3-(4-morpholine) propoxy)quinoline is an important intermediate for the synthesis of Foretinib, a c-Met kinase inhibitors. In this study, we provided a novel method for the synthesis of this compoundw. 4-Chloro-6-methoxy-7-(3-(4-morpholine)propoxy)quinoline was synthesized from 2-methoxy-5-nitrophenol via a six-step reaction: etherification reaction with 1-bromo-3-chloropropane in the presence of potassium carbonate and potassium iodide, then nucleophilic substitution reaction with morpholine. The etherification and the nucleophilic substitution were combined into one pot reaction. And then the target compound was obtained from reduction by iron powder, condensation with michloric acid, high temperature cyclization and chlorination. The total yield was 32.4%. The structures of all compounds were confirmed by MS and 1HNMR. This synthetic process has the advantages of simple steps, short time consuming, simple operation and high yield.

Key words: 4-chloro-6-methoxy-7-(3-(4-morpholine)propoxy)quinoline; Foretinib; c-met kinase inhibitors; antitumor; synthesis 

引用本文赵培培,王刚,张帆.4--6-甲氧基-7-[3-(4-吗啉基)丙氧基]喹啉的合成[J].化学试剂,202244(4)613-616.

 

 

度鲁特韦的合成工艺改进

 

侍笑娜1a,b ,刘建武*1a,b,刘涛2,严生虎1a,b ,张跃1a,b

沈介发1a,b ,马晓明1a,b ,辜顺林1a,b

(1.  常州大学a. 药学院;b. 石油和化工行业连续流技术工程实验室,江苏 常州 213164

2. 浙江万丰化工股份有限公司,浙江 绍兴 312073


摘要4-氯乙酰乙酸甲酯和甲醇钠为原料制备4-甲氧基乙酰乙酸甲酯,再由N,N-二甲基甲酰胺二甲基缩醛缩合,与氨基乙醛缩二甲醇加成、草酸二甲酯环合、氢氧化锂选择性水解得到重要的吡啶酮中间体,经脱醛基保护基,(R)-3-氨基-1-丁醇环化,2,4-二氟苄胺酰胺化,最后经氯化镁脱甲基得到度鲁特韦,目标产物结构经1HNMR13CNMR以及MS表征与文献报道的以麦芽酚或4-甲氧基乙酰乙酸甲酯为起始原料合成路线相比,采用一锅法合成1-(2,2-二甲氧基乙基)-5-甲氧基-6-(甲氧基羰基)-4-氧代-1,4-二氢吡啶-3-羧酸,该合成方法原料易得减少分离纯化步骤,具有效率高、成本低、绿色环保等优点。

关键词:度鲁特韦;4-甲氧基乙酰乙酸甲酯;吡啶酮;合成

中图分类号:TQ460.6      文献标识码:A     文章编号:0258-32832022--

 

Improvement of the Synthesis Process of Dolutegravir SHI Xiao-na1,2, LIU Jian-wu*1,2, LIU Tao3, YAN Sheng-hu1,2, ZHANG Yue1,2, SHEN Jie-fa1,2, MA Xiao-ming1,2, GU Shun-lin1,2 (1a. School of Pharmacy, b. Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry, Changzhou University, Changzhou 213164, China; 2. Zhejiang Wanfeng Chemical Co.Ltd., Shaoxing 312073, China), Huaxue Shiji, 2022, 44(4),

Abstract: Methyl 4-methoxyacetoacetate was synthesized with methyl 4-chloroacetoacetate and sodium methoxide as raw materials, then it was condensed with N,N-dimethylformamide dimethyl aceta, addition with aminoacetaldehy dedimethyl acetal, and aminoacetaldehyde dimethyl acetal. Important pyridine intermediate compounds were obtained from cyclization of dimethyl oxalate and selective hydrolysis of lithium hydroxide. After removing the aldehyde protecting group, they were cyclized with (R)-3-amino-1-butanol followed by being amidated with (2,4-difluorophenyl)methanamine and then demethylated by magnesium chloride to obtain dolutegravir. The structure of the product was characterized by 1HNMR, 13CNMR and MS. Compared with the synthetic route reported in literatures using maltol or methyl 4-methoxyacetoacetate as starting materials, a "one-pot method" was used to synthesize 1-(2,2-dimethoxyethyl)-5-methoxy-6-(methoxycarbonyl)-4-oxo-1,4-dihydropyridine-3-carboxylic acid by employing methyl 4-chloroacetoacetate as the starting material. The synthesis method has the advantages of easy-to-obtain raw materials, reduced separation and purification steps, high efficiency, low cost, and environmental protection.

Key words:dolutegravir; methyl 4-methoxyacetoacetate; pyridone; synthesis

引用本文:侍笑娜,刘建武,刘涛,等. 度鲁特韦的合成工艺改进[J]. 化学试剂,2022444617-622

 

 

轴手性酰基硫脲催化合成吡唑啉酮衍生物

杨兰西1,秦婷2,安雪婕2,陈治明*2

(贵州师范大学 化学与材料科学学院 贵州省功能材料化学重点实验室,贵州 贵阳 550001)

 

摘要吡唑啉酮环化合物具有生物药理活性等多种特性和用途而被认为是极具价值的结构基元之一吡唑环上易形成氢键等特性使得药物分子中的吡唑啉酮结构能够发挥生理活性合成了多种以BINOL为手性骨架、结构上下对称的新型多活性中心C2轴手性氢键型双酰基硫脲催化剂,将其用于催化合成吡唑啉酮衍生物。实验结果表明:在35 ℃下,以10 mol% (R)-N3, N3'-(4-甲基苯乙基)-2, 2'-二羟基-[1, 1'-联萘]-3, 3'-二甲酰基硫为催化剂,底物物质的量比为1∶1.510 mL CH2Cl2溶剂中回流反应24 h后,目标产物吡唑啉酮获得了良好的产率89%e.e.91%,并对底物进行了扩展,其范围较广,有较好的普适性。

关键词BINOL轴手性;酰基硫脲;5-氧代-1吡唑啉衍生物硝基乙烯

中图分类号O626.21             文献标识码A                文章编号0258-32832022

 

Synthesis of Pyrazolinone Derivatives Catalyzed by Axisymmetric Acylthioureas YANG Lan-xi1, QIN Ting2, AN Xue-jie2, CHEN Zhi-ming*2 (School of Chemistry and Materials Science, Guizhou Normal University, Key Laboratory of Functional Materials Chemistry of Guizhou Province, Guiyang 550001, China), Huaxue Shiji, 2022, 44(4)

Abstract: The pyrazolone ring compound has many characteristics and uses such as biopharmacological activity and is considered to be one of the most valuable structural elements. The pyrazolone structure in the drug molecule can exert its physiological activity due to the easy formation of hydrogen bonds on the pyrazolone ring. Therefore, a variety of novel multi-active center C2-axis chiral hydrogen-bonded bisacylthiourea catalysts (1a1c) were synthesized with BINOL as the chiral framework and the symmetrical structure, which were used to catalyze the synthesis of pyrazolone derivatives. The results show that the target product pyrazolone derivatives has a good yield of 89% with an ee value of 91% at 35 , with 10 mol% 1a as the catalyst and the substrate molar ratio 1:1.5, after the mixture being refluxed in 10 ml CH2Cl2 for 24 h. The substrate has been expanded, with a wider range and good universality.

Key words: BINOL axis chirality; acylthiourea; 5-oxo-1 pyrazoline derivative; nitroethylene

引用本文:杨兰西,秦婷,安雪婕,等. 轴手性酰基硫脲催化合成吡唑啉酮衍生物[J]. 化学试剂,2022444623-631

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