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    《化學試劑》2022年第4期中英文摘要(附整期文章PDF文檔)

    發布時間: 2022-04-08 13:22:11   試劑信息網

    N-磷?;被岬难芯窟M展和試劑化前景展望

    羅建紅,趙玉芬,倪鋒*

    (寧波大學 新藥技術研究院,浙江 寧波  315211

     

    摘要:磷是生命的重要元素之一,充分參與生命體的組成結構和各種生化反應。蛋白質磷?;瞧駷橹棺畛R姷姆g后修飾。氨基酸是蛋白質的基本結構模塊,其化學性質相對穩定。當氨基酸的氨基被磷?;瘯r,由于鄰近羧基的參與,該氨基酸易被活化成為具有多種生化活性的微型活化酶。在酸性條件下,N-磷?;被岬母吣?/span>P-N因為N原子容易質子化變得很不穩定,從而限制了N-磷?;被岬暮铣梢约?/span>作為化學試劑的應用。因此,探索適合于各種N-磷?;被岬母咝Ш铣煞椒ú⒄瓶仄浠瘜W活性具有潛在的應用價值。綜述了N-磷?;被岬姆诸?、合成方法以及化學性質等方面。同時,也討論了該領域中亟待解決的問題,并對其前景進行了展望。

    關鍵詞:磷;蛋白質磷?;?;氨基酸;N-磷?;被?;P-N

    中圖分類號: O627.51                  文獻標碼:A      文章編號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:羅建紅,趙玉芬,倪鋒. N-磷?;被岬难芯窟M展和試劑化前景展望[J]. 化學試劑,2022, 44(4):485-494.

     

    不同官能團改性殼聚糖吸附重金屬的研究進展

     

    劉義a,張淑琴*a,b,任大軍a,b,張曉晴a,b

    (武漢科技大學a. 資源與環境工程學院;b. 冶金礦產資源高效利用與造塊湖北省重點實驗室,湖北 武漢  430081

     

    摘要:殼聚糖作為一種儲量豐富,未得到充分利用的有機聚合物,其在重金屬吸附領域具有良好的應用前景。然而殼聚糖在酸性介質中易溶解、吸附選擇性差、吸附容量低等缺點限制了其進一步應用。近年來研究人員通過對殼聚糖進行改性來改善其缺點已取得一些成果。鑒于此,綜述了近幾年關于殼聚糖改性的相關研究,重點歸納總結了利用胺基、羧基、巰基以及雜環等改性修飾制備殼聚糖吸附劑的研究,并用表格的方式對比分析了不同殼聚糖基吸附劑的應用效果和吸附機理。進一步展望了殼聚糖基吸附劑未來的發展方向,為開發高效的重金屬離子吸附劑提供參考。 

    關鍵詞:殼聚糖;重金屬;官能團;廢水處理

    中圖分類號:X703      文獻標志碼:A      文章編號: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:劉義, 張淑琴, 任大軍, .不同官能團改性殼聚糖吸附重金屬的研究進展[J]. 化學試劑, 2022, 44(4): 495-503。

     

     

    基于光熱治療和光動力治療的光學療法用于腫瘤治療

     

    王剛1,2,3,雷夢穎3,周艷林1, 鄒節明*1, 奉建芳*2,3

    1. 桂林三金藥業股份有限公司,廣西 桂林541004;2. 江西中醫藥大學 藥學院,江西 南昌330004;

    3. 廣西壯瑤藥工程技術研究中心,廣西 南寧530200

     

    摘要:癌癥已經成為威脅人類健康的頭號殺手。盡管手術治療、放化療等手段成為臨床治療的主導,但是強侵入性以及不能忍受的毒副作用嚴重影響著患者的生活質量。因此,開發非侵入性、安全性高的光學治療意義重大。目前,基于無機和有機材料的腫瘤光動力治療(Photodynamic Therapy, PDT)和光熱治療(PhotothermalTherapy, PTT)研究取得了許多積極的成果。從光學治療的作用機制、PTTPDT抗腫瘤的應用進行綜述,會對更高效、更安全的光學治療提供一定的理論指導。

    關鍵詞:光動力治療;光熱治療;腫瘤;材料;聯合應用

    中圖分類號R94       文獻標識碼A文章編號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:王剛,雷夢穎,周艷林,等. 基于光熱治療和光動治療的光學療法用于腫瘤治療[J].化學試劑,2022,444):504-513.

     

     

    青蒿素及其衍生物的抗寄生蟲活性研究進展

     

    翟榮航,王合珍,王京,張磊*,徐應淑*

    遵義醫科大學 藥學院 貴州省生物催化與手性藥物合成重點實驗室,貴州 遵義  563000

     

    摘要青蒿素是一種從菊科蒿屬植物黃花蒿(Artemisia annua L.)中分離出來的倍半萜類天然產物,具有廣泛的生物活性,如抗腫瘤、抗炎、抗菌、抗惡性瘧原蟲等。青蒿素也是重要的抗瘧先導化合物,目前臨床上使用的青蒿素類抗瘧藥物有雙氫青蒿素、蒿甲醚、青蒿琥酯。近年來的研究發現,青蒿素及其衍生物對弓形蟲、血吸蟲、犬型孢子蟲、利什曼原蟲等多種病原體也具有廣泛的抑制活性。主要綜述近年來青蒿素及其衍生物抗蟲活性研究進展,期望對新型抗寄生蟲類青蒿素藥物的研發有所幫助。

    關鍵詞青蒿素;結構修飾;衍生物;抗寄生蟲;研究進展

    中圖分類號R284        文獻標識碼A      文章編號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

    引用本文翟榮航, 王合珍, 王京, .青蒿素及其衍生物的抗寄生蟲活性研究進展[J]. 化學試劑,2022,44(4)514-521.

     

     

    手性膽甾類熒光探針在食品檢測中對中性分子的識別研究 

     

    羅黎霞,馬文珍,劉哲,葉英*,韓麗娟

    (青海大學 農牧學院,青海 西寧  810016

     

    摘要利用紫外分光光度滴定法、Job法、熒光滴定法研究考察了手性膽甾類熒光探針分子鉗對有機酸、酚酸、含氮堿基的識別性能,并測定了主客體之間的結合常數和自由能變化值,建立了膽甾類熒光探針快速檢測有機酸、酚酸、含氮堿基的方法。研究結果表明,主體分子鉗與所考察丁香酸、香草酸、蘋果酸、熊果酸、沒食子酸、亞油酸、腺嘌呤、胞嘧啶均形成1:1型靜態淬滅超分子配合物。并將該方法應用于香蘭莢豆香草酸、小米糠油亞油酸、豬肝腺嘌呤的檢測;檢測結果表明,香蘭莢豆中香草酸的含量為0.148 mg/g、小米糠油中亞油酸的含量為70 mg/g、豬肝中腺嘌呤的含量為81 mg/100g。

    關鍵詞膽甾;分子識別;有機酸;酚酸;含氮堿基

    中圖分類號:063              文獻標志碼:A      文章編號: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:羅黎霞,馬文珍,劉哲,等. 手性膽甾類熒光探針在食品檢測中對中性分子的識別研究[J]. 化學試劑, 2022: 44(4), 522-530。

     

     

    型近紅外氧雜蒽熒光染料用于線粒體熒光成像

    曾紅,郭小美,朱玉蓮,練萍,范小林,吳勇權*

    (贛南師范大學 化學化工學院 江西省有機藥物化學重點實驗室,江西 贛州  341000

     

    摘要:熒光成像具有操作簡單、靈敏度高和實時等優點,而近紅外熒光成像能夠有效避免生物組織自發熒光干擾。通過設計和合成3個新型近紅外氧雜蒽熒光染料NXD-1NXD-3用于細胞熒光成像。首先,3個氧雜蒽熒光染料分子結構得到核磁共振譜和高分辨質譜的確認。其次,詳細研究了這些熒光染料的吸收光譜和熒光光譜,實驗數據表明3熒光染料的發射光譜能夠達到近紅外區域,其中NXD-3的光譜更為紅移,它的最大吸收和發光波長分別為611 nm759 nm。另外,密度泛函理論(DFT)計算結果與實際測試光譜數據相匹配。最后,將制備的氧雜蒽熒光染料用于細胞熒光染色成像,實驗結果表明熒光染料NXD-3具有良好的細胞線粒體靶向熒光標記效果。

    關鍵詞氧雜蒽;近紅外;線粒體;熒光染料;熒光成像

    中圖分類號O625.15        文獻標識碼A          文章編號: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

    引用本文曾紅,郭小美,朱玉蓮, . 新型近紅外氧雜蒽熒光染料用于線粒體熒光成像[J]. 化學試劑,2022,44(4): 531-537。

     

     

    基于四苯基乙烯-羅丹明的HClO/ClO-可視化熒光探針的合成及性質研究

    張珍,陳佳敏,來素涵,曾竟*,李佳佳

    新疆師范大學 化學化工學院,新疆 烏魯木齊  830054

     

    摘要:次氯酸(HOCl)/次氯酸鹽(ClO-)作為一種強氧化劑應用廣泛,在機體免疫防御中起著至關重要的作用,過量HOCl/ClO-對環境及人體造成潛在威脅,因此,建立可靠、精準檢測HOCl/ClO-的分析方法具有重要意義。通過縮合、還原兩步合成得到具有聚集誘導性質的四苯基乙烯-羅丹明類衍化合物TPE-RhB2,探針TPE-RhB2在乙醇/水溶液中實現了對ClO-的可視化熒光識別,在505 nm處熒光發生猝滅,猝滅比為90.2%,同時在572 nm處出現一新的熒光發射峰。該探針在pH 1~12內熒光響應穩定,并具有較強的抗干擾能力和靈敏度,檢出限低至5.32 × 10-7 mol/L,Stokes位移高達155 nm,有望在復雜環境中實現對ClO-的檢測。通過ESI-MS譜初步確定ClO-通過氧化水解機制引起了熒光信號和探針溶液顏色變化,根據所建分析方法實現了實際水樣中ClO-的檢測。

    關鍵詞:四苯乙烯;羅丹明B;聚集誘導發光;HClO/ClO-熒光探針

    中圖分類號:O621.2             文獻標識碼:A           文章編號: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

    引用本文張珍,陳佳敏,來素涵,等. 基于四苯基乙烯-羅丹明的HClO/ClO-可視化熒光探針的合成及性質研究[J]. 化學試劑,2022,44(4):538-543。

     

     

    偶氮基雙核鈷配合物的合成、結構及光學性質

    潘昊,陳琪騏,謝燕婷,梁曉彤,盧子豪,邱燕璇*

    廣東第二師范學院 化學與材料科學學院,廣東 廣州  510303

     

    摘要室溫下,通過調控反應體系的pH值,構筑了一例新的基于5-偶氮四唑水楊酸(H3ASA)的鈷配合物[Co2(HASA)2(H2O)6] (1),并借助X-射線單晶衍射解析其晶體結構。結果顯示,配合物1結晶于單斜晶系,P21/c空間群,每個不對稱單元由兩個Co(II)離子,兩個HASA2-配體以及6個配位水分子組成。晶體結構中,中心離子Co(II)六配位八面體構型,配體HASA2-橋聯兩個不同的Co(II)離子形成雙核結構,鄰近的雙核單元通過OH×××O、OH×××NCH×××O 3種氫鍵相互作用形成3D超分子結構。合物在室溫下穩定,研究表明配合物在365 nm波長輻照展現出光致異構性質,在302 nm光激發下發出紫色熒光。

    關鍵詞偶氮化合物;晶體結構;鈷;光致異構;熒光

    中圖分類號:O614    文獻標識碼:A       文章編號: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,陳琪騏,謝燕婷,等. 偶氮基雙核鈷配合物的合成、結構及光學性質[J]. 化學試劑,2021,44(4):544-549。

     

     

    三維網狀化合物[(H2DABCO)CaCl4(H2O)2]的合成、結構及性能

     

    胡宏志a,劉洋*a,b,劉穎a,徐慧婷a,劉尊奇*a,b

    (新疆農業大學 a. 化學工程學院,b. 新疆農業化學生物材料重點實驗室,新疆 烏魯木齊  830052

     

    摘要:1,4-二氮雜二環[2,2,2]辛烷(DABCO)、氯化鈣、鹽酸以一定比例溶入甲醇溶液,通過自然蒸發方式獲得一種具有三維網狀結構的新穎有機-無機雜化化合物[(H2DABCO)CaCl4(H2O)2],以紅外光譜(IR)、元素分析、單晶X衍射、X-射線粉末衍射、熱重分析(TG)、變溫-變頻介電等測試,確定化合物的結構及性能。結果顯示,化合物在低溫(100 K)和室溫(296 K)下空間群為P-1,屬于三斜晶系,晶胞內[CaCl4(H2O)2]2-陰離子八面體結構發生變形,尤其是陰陽離子間的氫鍵相互作用改變導致所形成的三維網狀結構發生明顯的伸縮震動,致使化合物在a、b軸方向上225 ~ 265 K溫度范圍內產生顯著的介電異?,F象。

    關鍵詞:1. 4-二氮雜二環[2,2,2]辛烷;氫鍵;三維網狀結構;介電異常

    中圖分類號: O612.2             文獻標識碼:  A                    文章編號: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, 劉洋, 劉穎, 等.三維網狀化合物[(H2DABCO)CaCl4(H2O)2]的合成、結構及性能[J].化學試劑, 2022, 444550-556.

     

     

    超聲波輔助雙水相體系優化橘紅花總黃酮提取工藝及其抗氧化活性

     

    臧青民a,b,李秋珊a,徐燕波a,蔣德旗a,李海東a,章燁雯*a,b

    玉林師范學院a. 生物與制藥學院,b. 特色農林植物種質資源創新與應用研究中心,廣西 玉林 537000

     

    摘要:以總黃酮得率為響應值,采用響應面法優化超聲波輔助雙水相體系提取橘紅花總黃酮工藝,并評估其抗氧化活性。在單因素實驗基礎上,選取乙醇濃度、硫酸銨濃度、超聲溫度為考察因素,采用Box-Behnken響應面分析法建立回歸模型,篩選最佳提取工藝條件,并研究其清除DPPHABTS+自由基的能力。結果表明,超聲波輔助雙水相體系提取橘紅花總黃酮的最佳條件為:乙醇濃度55%、硫酸銨濃度為0.3 g/mL,超聲溫度50℃,超聲時間30 min,液料比為20:1mL/g)。在此提取條件下,所得橘紅花總黃酮得率為5.03%,與預測值較接近??寡趸瘜嶒灲Y果表明,橘紅花總黃酮對DPPHABTS+自由基的IC50分別為0.1240.173mg/mL,與維生素C相比,抗氧化活性較弱。采用Box-Behnken響應面法優化的橘紅花總黃酮提取工藝穩定可靠,可用于橘紅花總黃酮的提??;橘紅花總黃酮具有較強的抗氧化活性,為橘紅花總黃酮的研究和開發利用提供了實驗基礎。

    關鍵詞:橘紅花;總黃酮;響應面法;超聲波;雙水相提??;抗氧化活性

    中圖分類號R284.2       文獻標識碼:A      文章編號: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 min,solvent-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.超聲波輔助雙水相體系優化橘紅花總黃酮提取工藝及其抗氧化活性[J]. 化學試劑, 2022, 44(4):557-563。

     

     

    基于NO2的分離與富集光度法測定水中痕量NO2-

    王春雨,李曉惠*,田亞賽,劉靜璇,劉恩,許艷廣

    (遼寧科技學院 藥化學院,遼寧 本溪  117004)

     

    摘要在檸檬酸-乙醇介質中,NO2-被迅速轉化成NO2,利用吹氣分離法將其轉移至凈化空氣中;凈化空氣中的NO2與吸收液中的對氨基苯磺酸N-(1-萘基)乙二胺鹽酸鹽發生顯色反應進而被富集,據此,水中痕量NO2-可采用分光光度法在540 nm波長處被間接測定。當采用三級吸收,A= A1+A2+A3作為響應值,在擬定的實驗條件下,NO2-轉化系數83.5%,富集倍數10,方法的測定線性范圍3.066.7 μg/L之間。本方法有效消除了色度、濁度、鹽分對NO2-測定的干擾,檢出限為0.9 μg/L,是國標法(GB 7493-87的十分之一,用于井水、溪水中NO2-的測定,RSD2.9%,回收率在96.6%102.2%之間,表明該方法適用于測定水中痕量NO2-。

    關鍵詞NO2-;吹氣分離;富集;分光光度法;測定

    中圖分類號: O65       文獻標識碼: A     文章編號: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 Engineering,Liaoning Institute of Science and Technolgy,Benxi 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,李曉惠,田亞賽,等. 基于NO2的分離與富集光度法測定水中痕量NO2[J]. 化學試劑,2022,44(4): 564-568。

     

     

    微波輔助制備巴旦木殼吸附劑對活性艷紅X-B吸附性能研究

    張建,陳彥萍,李小敏*

    (伊犁師范大學 化學與環境科學學院,污染物化學與環境治理重點實驗室,新疆 伊寧 835000

     

    摘要:以新疆厚皮原味巴旦木去仁所得殼作為原料進行實驗,以0.7 mol/L的氯化鋅活化制成活性炭。探索在各類波條件下,各種因素對巴旦木殼吸附活性艷紅X-B的影響。微波協同巴旦木殼活性炭吸附劑對活性艷紅X-B染料吸附有一定的效果,最佳吸附條件是0.5 g活性炭,100 mg/L活性艷紅X-B染料,輻射時間2 min。吸附過程符合準二級動力學方程,是化學吸附。經過對比發現Langmuir吸附等溫式擬合效果明顯,是單分子層吸附。正交實驗得出吸附量優化組合:t=1 min,m=0.6 g,c=300 mg/L。去除率組合:t=3 min,m=0.6 g,c=100 mg/L。極差分析得出,吸附量優化組合:t=2 min,m=0.6 g,c=300 mg/L。影響順序:染料濃度大于吸附劑用量大于吸附時間。去除率的優化組合:t=3 min,m=0.6 g,c=300 mg/L。影響順序:染料濃度大于吸附劑用量大于吸附時間。方差分析得出,吸附量的影響順序:染料濃度影響最大,吸附劑用量次之,吸附時間影響最小。去除率的影響順序為染料濃度最大,吸附劑用量次之,吸附時間對實驗結果影響不大。

    關鍵詞巴旦木殼;活性炭;活性艷紅X-B;吸附性能;微波

    中圖分類號:TQX703.1      文獻標識碼:A      文章編號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:張建,陳彥萍,李小敏. 微波輔助制備巴旦木殼吸附劑對活性艷紅X-B吸附性能研究[J].化學試劑,2022,444):569-576.

     

     

    不同氧化劑對土壤中有機氯農藥γ-HCH降解效果的影響

     

    項文霞*1,李義連2,李釗3,陳金國1

    1. 湖北省地質局第三地質大隊,湖北 黃岡438000;2.中國地質大學(武漢) 環境學院,湖北 武漢430074;

    3. 黃州區自然資源和規劃局,湖北 黃岡438000

     

    摘要有機氯農藥γ-HCH殺蟲活性強,化學性質穩定,在環境中不易降解,殘留期長,對生態環境和人體危害嚴重。通過加速溶劑萃取法聯合氣相色譜法,研究了Fenton試劑、熱活化的Na2S2O8對土壤中有機氯農藥γ-HCH的降解效果。結果表明,Fenton試劑和Na2S2O8在氧化降解γ-HCH方面都表現出很高的活性。當水土質量比為2.5 : 1,反應溫度為25 oC,Fe2+H2O2投加量分別為0.2 mmol10 mmol時,γ-HCH去除率為88%;當水土質量比為2.5 : 1,反應溫度為50 oC,Na2S2O8投加量為5 mmol時,γ-HCH去除率為91.78%。使用Fenton試劑和Na2S2O8分別作為氧化劑對γ-HCH的去除均符合準一級反應動力學模型,其反應速率和去除率與水土比、反應溫度、氧化劑投入量等因素有關。在優化后的反應條件下,使用Na2S2O8氧化降解γ-HCH的反應速率常數和反應半衰期分別為0.003 min-13.85 h;相較于Fenton試劑,其反應速率常數提高了約50%,反應半衰期縮短了約35%。

    關鍵詞Fenton試劑;Na2S2O8;γ-HCH;脫氯;氧化降解;反應動力學

    中圖分類號X53    文獻標識碼A      文章編號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:項文霞, 李義連, 李釗, . 不同氧化劑對土壤中有機氯農藥γ-HCH降解效果的影響[J].化學試劑,444577-583.

     

     

    氣相色譜質譜聯用測定植物油中的非皂化物質

    王建鑫,曹旭妮*

    華東理工大學 食品科學與工程系,上海 200237

     

    摘要:建立了測定植物油中的非皂化成分(角鯊烯及甾醇物質的氣相色譜質譜聯用分析方法,其檢測限均小于2.00 mg/L,加標回收率為90.12%112.42%。采用該方法實現了山茶油、大豆油和玉米油的非皂化物質的含量分析。同時,通過分析還表明,山茶油中的豆甾醇大豆油或玉米油)中的存在顯著差異,β-谷甾醇大豆油與玉米油也存在顯著差異,提示它們可能是防偽分析的重要參數。所建立的方法具有高效、準確和靈敏的優點,這將為今后用于構建動態數據庫用于綜合評價植物油提供了一種分析方法。

    關鍵詞:氣相色譜質譜聯用法;甾醇;角鯊烯;植物油

    中圖分類號O657.7    文獻標識碼A      文章編號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. 氣相色譜質譜聯用測定植物油中的非皂化物質[J]. 化學試劑, 2022, 44(4): 584-589。

     

     

    UHPLC快速測定豆漿粉中大豆異黃酮

    李永利*,李杰,姜陽,吳建軍,薛

    上海市計量測試技術研究院 理化分析室 在線檢測與控制技術重點實驗室,上海  201203

     

    摘要:為了同時測定豆漿粉中多種大豆異黃酮成分,建立了一種豆漿粉中大豆異黃酮的超高效液相色譜分析方法。樣品由80%乙醇水溶液超聲提取,經堿性條件皂化反應獲得大豆異黃酮測試溶液。色譜柱采用Waters Atlantis T3,流動相為0.1%甲酸/水溶液-乙腈,梯度洗脫,流速為0.6 mL/min,DAD檢測器分析波長為260 nm。測定方法采用外標法定量,3個濃度下加標回收率為93.80% 97.99%,相對標準偏差(RSD<3.5%,檢出限為0.4 0.5 mg/kg。方法重現性好,適合豆漿粉基質中大豆異黃酮的快速測定。

    關鍵詞:大豆異黃酮;液相色譜;豆漿粉;含量測定

    中圖分類號: O657.7      文獻標示碼: A         文章編號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,姜陽,等.UHPLC快速測定豆漿粉中大豆異黃酮[J].化學試劑,2022,444590-593.

     

     

    超高效液相色譜串聯質譜法測定中藥保健品中6種有毒生物堿

    許曉輝1,王瑞1,黨子龍2,王小喬*1,張虹艷1,潘秀麗1,李晨曦1,李赟1

    (1. 蘭州市食品藥品檢驗檢測研究院,甘肅 蘭州 730050;2. 蘭州大學第一醫院藥劑科,甘肅 蘭州  730000

     

    摘要建立了QuEChERS法凈化,超高效液相色譜串聯三重四極桿質譜UPLC-MS/MS測定中藥類保健品中6種有毒生物堿含量的方法。樣品以1%甲酸乙腈超聲提取,BEH C18色譜柱(1.7 μm,2.1 mm×100 mm)分離,以0.1%甲酸-2 mmol/L乙酸銨的水溶液與含0.1%甲酸的乙腈溶液為流動相梯度洗脫,三重四極桿質譜正離子多反應監測模式檢測(MRM),外標法定量。在優化的色譜質譜條件下,6種生物堿在020 ng/mL線性關系良好,相關系數均大于0.9942。方法檢出限(LOD,S/N=3)為0.0020.05 μg/kg,定量限(LOQ,S/N=10)為0.0070.15 μg/kg,在2、5、10 μg/kg的加標濃度下,6種目標分析物的平均回收率范圍為62.3%98.2%,相對標準偏差(RSD)為1.6%3.6%。該方法準確、高效、簡便,適用于中藥保健品中有毒生物堿的定性定量篩查。

    關鍵詞中藥;保健品;超高效液相色譜串聯質譜法;生物堿;有毒;測定

    中圖分類號R917      文獻標識碼A       文章編號: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, China;2. 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:許曉輝,王瑞,黨子龍,等. 超高效液相色譜串聯質譜法測定中藥類保健品中6種有毒生物堿[J]. 化學試劑,2022,444594-598.

     

     

    穩定同位素氘標記鹽酸曲托喹酚的制備

    秦爽1,韓世磊1,2,邵文哲1,徐銀1,2,石靜飛1,2,佟慶龍1,2,張磊*1,2

    1. 天津阿爾塔科技有限公司,天津  300457;2. 阿爾塔標準物質研究院,天津  300457

     

    摘要:2-3,4,5-三甲氧基苯基)乙酸為起始原料,經過脫甲基、酰胺化、甲基化、比希勒-納皮拉爾斯基(Bischler-Napieralski)環化反應、還原、脫保護基等關鍵反應步驟,得到穩定同位素氘標記的鹽酸曲托喹酚。該合成方法原料廉價易得、簡單成熟,目標產物氘同位素豐度較高。該產物經核磁共振氫譜(1HNMR)和高分辨質譜(HR-MS)表征確認,氘同位素豐度為99.9 atom%D,適合作為內標試劑用于曲托喹酚的定性定量分析。

    關鍵詞:穩定同位素標記;氘標記鹽酸曲托喹酚;質譜內標試劑;同位素豐度

    中圖分類號:O628.1    文獻標識碼A      文章編號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, China;2. 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 cheap,accessible 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 abundance;isotope abundance

    引用本文秦爽,韓世磊,邵文哲,等. 穩定同位素氘標記鹽酸曲托喹酚的制備[J]. 化學試劑,2022,44(4):599-603。

     

     

    標記克倫丙羅的合成方法研究與結構表征

    曹煒東1,韓世磊1, 2,馬秀婷1,徐銀1, 2,石靜飛1, 2,佟慶龍1, 2,張磊*1, 2

    1. 天津阿爾塔科技有限公司,天津  300457;2. 阿爾塔標準物質研究院,天津  300457

     

    摘要穩定同位素內標試劑與同位素稀釋質譜法相結合的檢測技術,為快速準確地檢測β2-受體激動劑克倫丙羅的含量提供了可能。報道了一種新型的穩定同位素氘標記克倫丙羅的合成方法,以4-氨基-3,5-二氯-α-溴代苯乙酮為原料,經改良的Gabriel方法合成了伯胺化合物,再與丙酮-D6經還原胺化反應制備了穩定性同位素標記的克倫丙羅-D7,具有路線短、操作簡便、總產率高等優點。該產物經核磁共振氫譜(1HNMR)和質譜(ESI-MS)表征確認,氘同位素豐度可達98.3 atom%,可作為質譜內標試劑應用于獸殘檢測領域。

    關鍵詞:穩定同位素標記;克倫丙羅-D7;內標試劑;獸殘檢測

    中圖分類號:TQ463.7      文獻標識碼:A     文章編號:

     

    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, China;2. 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

    引用本文曹煒東,韓世磊,馬秀婷,等. 氘標記克倫丙羅新的合成方法研究與結構表征[J]. 化學試劑, 2022, 44(4):604-607。

     

     

    鹽酸萊克多巴胺-D6新的合成方法研究與結構表征

    劉曉佳1,韓世磊1, 2,孔香玲1,徐銀1, 2,石靜飛1, 2,佟慶龍1, 2,張磊*1, 2

    1. 天津阿爾塔科技有限公司,天津  300457;2. 阿爾塔標準物質研究院,天津  300457

     

    摘要:穩定同位素內標試劑與同位素稀釋質譜法相結合的檢測技術,為快速準確地檢測萊克多巴胺的含量提供了可能。以4-(4-甲氧苯基)-2-丁酮為起始原料,經氫-氘交換、還原胺化、脫保護基反應,合成穩定同位素氘標記的鹽酸萊克多巴胺。這條新的合成路線,具有路線短、操作簡便、原料廉價易得等優點。合成產物經核磁共振氫譜(1HNMR)和質譜(ESI-MS)表征確認,氘同位素豐度97.7 atomD??勺鳛橘|譜內標試劑應用于獸殘檢測領域。

    關鍵詞:穩定同位素標記;氘標記萊克多巴胺;氫-氘交換反應;質譜內標試劑

    中圖分類號:O625.63    文獻標識碼:A     文章編號: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, China;2. 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 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:劉曉佳,韓世磊,孔香玲,等. 鹽酸萊克多巴胺-D6新的合成方法研究與結構表征[J].化學試劑,2022,44(4):608-612。

     

     

    4--6-甲氧基-7-[3-(4-嗎啉基)氧基]喹啉的合成

     

    趙培培,王剛,張帆*

    (錦州醫科大學 藥學院,遼寧 錦州  121001

     

    摘要4--6-甲氧基-7-[3-(4-嗎啉基)氧基]喹啉是合成c-met激酶抑制劑Foretinib的重要中間體。2-甲氧基-5-硝基苯酚為原料,在碳酸鉀及碘化鉀存在下與1--3-氯丙烷發生醚化反應,然后再與嗎啉發生親核取代反應,且將醚化及親核取代兩步反應合為一鍋反應。再經鐵粉還原、與米氏酸縮合、高溫環合、氯代共6反應制得目標化合物,反應總收率為32.4%。所有化合物結構經MS1HNMR進行確證。該路線步驟簡潔、耗時短、操作簡單,收率較高。

    關鍵詞4--6-甲氧基-7-[3-(4-嗎啉基)氧基]喹啉;Foretinib;c-met激酶抑制劑;抗腫瘤;合成

    中圖分類號O625         文獻標識碼A          文章編號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 

    引用本文趙培培,王剛,張帆.4--6-甲氧基-7-[3-(4-嗎啉基)丙氧基]喹啉的合成[J].化學試劑,2022,44(4)613-616.

     

     

    度魯特韋的合成工藝改進

     

    侍笑娜1a,b ,劉建武*1a,b,劉濤2,嚴生虎1a,b ,張躍1a,b ,

    沈介發1a,b ,馬曉明1a,b ,辜順林1a,b

    (1.  常州大學a. 藥學院;b. 石油和化工行業連續流技術工程實驗室,江蘇 常州 213164;

    2. 浙江萬豐化工股份有限公司,浙江 紹興 312073


    摘要4-氯乙酰乙酸甲酯和甲醇鈉為原料制備4-甲氧基乙酰乙酸甲酯,再由N,N-二甲基甲酰胺二甲基縮醛縮合,與氨基乙醛縮二甲醇加成、草酸二甲酯環合、氫氧化鋰選擇性水解得到重要的吡啶酮中間體,經脫醛基保護基,(R)-3-氨基-1-丁醇環化,2,4-二氟芐胺酰胺化,最后經氯化鎂脫甲基得到度魯特韋,目標產物結構經1HNMR、13CNMR以及MS表征。與文獻報道的以麥芽酚或4-甲氧基乙酰乙酸甲酯為起始原料合成路線相比,采用一鍋法合成1-(2,2-二甲氧基乙基)-5-甲氧基-6-(甲氧基羰基)-4-氧代-1,4-二氫吡啶-3-羧酸,該合成方法原料易得,減少分離純化步驟,具有效率高、成本低、綠色環保等優點。

    關鍵詞:度魯特韋;4-甲氧基乙酰乙酸甲酯;吡啶酮;合成

    中圖分類號:TQ460.6      文獻標識碼:A     文章編號: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,劉建武,劉濤,等. 度魯特韋的合成工藝改進[J]. 化學試劑,2022,444617-622。

     

     

    軸手性?;螂宕呋铣蛇吝?/span>啉酮衍生物

    楊蘭西1,秦婷2,安雪婕2,陳治明*2

    (貴州師范大學 化學與材料科學學院 貴州省功能材料化學重點實驗室,貴州 貴陽 550001)

     

    摘要吡唑啉酮環化合物具有生物藥理活性等多種特性和用途而被認為是極具價值的結構基元之一,吡唑環上易形成氫鍵等特性使得藥物分子中的吡唑啉酮結構能夠發揮生理活性。合成了多種以BINOL為手性骨架、結構上下對稱的新型多活性中心C2軸手性氫鍵型雙?;螂宕呋瘎?,將其用于催化合成吡唑啉酮衍生物。實驗結果表明:在35 ℃下,以10 mol% (R)-N3, N3'-(4-甲基苯乙基)-2, 2'-二羥基-[1, 1'-聯萘]-3, 3'-二甲?;?/span>為催化劑,底物物質的量比為1∶1.5,10 mL CH2Cl2溶劑中回流反應24 h后,目標產物吡唑啉酮獲得了良好的產率89%e.e.91%,并對底物進行了擴展,其范圍較廣,有較好的普適性。

    關鍵詞BINOL軸手性;?;螂?;5-氧代-1吡唑啉衍生物;硝基乙烯

    中圖分類號O626.21             文獻標識碼A                文章編號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:楊蘭西,秦婷,安雪婕,等. 軸手性?;螂宕呋铣蛇吝蜻苌?/span>[J]. 化學試劑,2022,444623-631。

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