CeO2纳米酶活性与抗菌性能研究进展
郭佳靖，高艳芳，张欣*
（内蒙古工业大学 化工学院，内蒙古 呼和浩特 010051）
摘要：近年来，细菌多重耐药性（Multidrug Resistance，MDR）现象日益严重，已威胁到人类健康。纳米材料的出现，为这一难题的解决带来希望。其中，二氧化铈纳米颗粒（Cerium Oxide Nanoparticles，CeO2 NPs）作为一种新型抗菌剂，具有生产成本低、结构稳定性高、催化活性可调、生物安全性高等优点，因而具有重要研究价值。根据Ce3+与Ce4+含量比值变化，CeO2 NPs可表现出不同纳米酶活性，进而可调节生物体内活性氧（Reactive Oxygen Species，ROS）自由基的水平，从而有效杀死细菌，破坏其细胞结构。综述了CeO2 NPs用于多种模式微生物的抗菌性能，阐述其抗菌机理，分析不同因素对其抗菌性能的影响，并对其在抗菌领域的应用前景进行展望，期望对抗菌剂的开发和应用提供更多参考。
关键词：二氧化铈纳米颗粒；抗菌机理；纳米酶活性；活性氧物种；耐药性
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2022）
The Application Progress of Cerium Oxide Nanozyme Activities and Antibacterial Properties GUO Jia-jing, GAO Yan-fang, ZHANG Xin* (College of Chemical Engineering, Inner Mongolia University of Technology, Inner Mongolia Hohhot, 010051, China), Huaxue Shiji, 2022,44（9）
Abstract: In recent years, bacterial multidrug resistance (MDR) has become increasingly serious, which has threatened human health. The emergence of nanomaterials brings hope for the solution of this difficult problem. Cerium oxide nanoparticles (CeO2 NPs) as a new antibacterial agent, has the advantages of low production cost, high structural stability and adjustable catalytic activity and thus shows substantial research value. CeO2 NPs show different enzyme activities according to the content of Ce3+ and Ce4+, which then could regulate the level of reactive oxygen species (ROS) free radicals, so as to effectively kill bacteria and destroy their cell structure. In this review, we mainly summarize the reports on antibacterial performance of CeO2 NPs against various model bacteria, and its antibacterial mechanism is elaborated in detail. The effects of diversely influence factors on antibacterial properties were also discussed. Finally, the application prospect of this antibacterial material was put forward, wishing to provide more reference for the development and application of antibacterial agents.
Key words: cerium oxide nanoparticles; antibacterial mechanism; enzyme-like activity; reactive oxygen species; drug resistanc
引用本文：郭佳靖, 高艳芳, 张欣. CeO2纳米酶活性与抗菌性能研究进展[J]. 化学试剂, 2022,44（9）:1249-1256.
植物酯酶应用于农药残留检测的研究进展
罗俊霞1，赵建波*2，张洁*2，张刚3，刘青4，潘玲1，马蕾2，王倩2，张威3
（1.郑州市农产品质量检测流通中心，河南 郑州 450006；2.郑州市农业技术推广中心，河南 郑州 450002；3.河南恒晟检测技术有限公司，河南 新郑 451100；4.郑州市农业综合行政执法支队，河南 郑州 450002）
摘要：为了全面了解植物酯酶在农药残留快速检测中的应用，通过阅读大量国内外相关文献，从植物酯酶及其制备、纯化、固定方法，植物酯酶对各种条件的筛选及其应用于农药残留检测时检测结果的准确性及预防措施等几方面进行了归纳，总结了植物酯酶应用于农药残留检测新方法，指出了植物酯酶应用于农药残留检测存在的问题。尽管如此，由于酶抑制法可对农药残留进行高通量快速筛查，植物酯酶又具有较高的性价比，因此，该酶具有无可取代的地位和作用。呼吁尽快制定植物酯酶抑制法农药残留快速检测试剂的制备标准，促使植物酯酶更好地应用于农药残留快速检测工作中。
关键词：植物酯酶；酶活；酶抑制法；快速检测；农药残留
中图分类号：O656.31 文献标识码：A 文章编号：0258-3283（2022）
Research Progress of Plant Esterase in the Detection of Pesticide Residues LUO Jun-xia1, ZHAO Jian-bo*2, ZHANG Jie*2, ZHANG Gang3, LIU Qing4, PAN Ling1, MA Lei2, WANG Qian2 ，ZAHNG Wei3(1. Zhengzhou Agricultural Product Quality Testing and Distribution Center, Zhengzhou 450006, China; 2. Zhengzhou Agricultural Technology Extension Centre, Zhengzhou 450006, China; 3.Henan Hengsheng Testing Technology Co., Ltd., Xinzheng 451100, China; 4. Zhengzhou Agricultural Comprehensive Administrative Law Enforcement Detachment, Zhengzhou 450002, China), Huaxue Shiji,
Abstract: In order to fully understand the application of plant esterase in the rapid detection of pesticide residues, we summarized the methods for preparation, purification and fixation of plant esterase, and the screening of various conditions and the accuracy of sensing results and preventive strategies of plant esterase when applied for the detection of pesticide residues on the basis of a large number of related literature at home and abroad in this review. Moreover, the new methods of applying plant esterase for the detection of pesticide residues were summed up, and their existing problems in the application of plant esterase to the detection of pesticide residues were discussed as well. Nevertheless, the plant esterase has an irreplaceable position and role due to its cost-effective performance as well as high-throughput screening of pesticide residues by enzymatic inhibition method. In the purpose of promoting the application of plant esterase in the rapid detection of pesticide residues, it is significant to set industrial chain standard for rapid detection of pesticide residues by plant esterase inhibition.
Key words: plant esterase; the activity of enzyme; enzyme inhibition method; rapid detection; pesticide residue
引用本文：罗俊霞，李润培，赵建波，等.植物酯酶应用于农药残留检测的研究进展[J].化学试剂，2022，44（9）:1257-1265.
NO供体型丹皮酚氧异丁酸硝酸酯类衍生物的合成及降血脂活性研究
李光耀1，陈诚1，卞在东1，刘鹏1，徐淼焱1，黄鹏*1,2
（1.安徽中医药大学 药学院，安徽 合肥 230012；2.中药研究与开发安徽省重点实验室，安徽 合肥 230012）
摘要：以丹皮酚为先导化合物，与α-溴代异丁酸通过Willamson合成法得到丹皮酚氧异丁酸，与不同碳数的二溴烷烃生成丹皮酚氧异丁酸溴代烷基酯中间体，再与硝酸银反应得到5个目标化合物。目标化合物结构经核磁共振氢谱、红外光谱和质谱确证。采用HepG2高血脂细胞实验、脂肪酶活性抑制和胆酸盐结合能力实验对所得化合物进行活性研究。实验结果表明目标化合物降血脂活性高于丹皮酚，其中丹皮酚氧异丁酸硝氧乙基酯活性最好，其升高HDL-C能力高于非诺贝特。当目标化合物浓度为5 mg/mL时，脂肪酶抑制率可达40%左右，对甘氨胆酸钠（SG）、牛黄胆酸钠（ST）的结合率可达80%左右。
关键词：丹皮酚；苯氧芳酸；合成；降血脂活性
中图分类号：TQ460.1 文献标识码：A 文章编号：0258-3283(2022)
Synthesis and Hypolipidemic Activity of NO-donating Paeonoloxyisobutyrate Nitrate Derivatives LI Guang-yao1, CHEN Cheng1, BIAN Zai-dong1, LIU Peng1，XU Miao-yan1, HUANG Peng*1,2 (1.School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012, China; 2.Anhui Province Key Laboratory of Research & Development of Chinese Medicine, Hefei 230012, China) , Huaxue Shiji，2022，44 (9)，00 ~ 00
Abstract：Paeonol oxyisobutyric acid was synthesized from paeonol and α-bromoisobutyric acid by Willamson method, and then reacted with dibromoalkanes with different carbon numbers to form paeonol oxyisobutyric acid alkyl ester intermediate. The intermediate is then reacted with silver nitrate to obtain five target compounds The structure of the target compound was confirmed by 1HMNR, IR and MS. The target compounds were subjected to activity studies by using HepG2 hyperlipidemia assay, lipase activity inhibition and cholate binding capacity assay. The HepG2 experimental results showed that the lipid-lowering activities of target compounds were higher than that of paeonol, among which 3a had the best activity. Moreover, the ability to increase HDL-C of target compound was higher than that of fenofibrate, and the inhibition rate of lipase was about 40%, the binding rate to sodium glycocholate (SG) and sodium taurocholate (ST) can reach about 80%, when the concentration of target compound was 5 mg/mL.
Key words：paeonol; phenoxyaromatic acid; synthesis; hypolipidemic activity
引用本文：李光耀，陈诚，卞在东，等. NO供体型丹皮酚氧异丁酸硝酸酯类衍生物的合成及降血脂活性研究 [J]. 化学试剂, 2022, 44(9): 1266-1271。
基于Click反应的5-氟尿嘧啶与4-苯胺喹唑啉骨架的拼接合成及其抗肿瘤活性评价
梁光平1，杨杰1，梁光焰2，王道平2，杨俊*1
(1. 遵义医药高等专科学校 药学系，贵州 遵义 563006；2. 贵州省中国科学院天然产物化学重点实验室，贵州 贵阳 550014)
摘要：以3种羟基喹唑啉-4-酮为原料，经乙酰化、氯化、取代、水解、烷基化反应得到6个末端含有端炔取代的4-苯胺喹唑啉类化合物，同时以5-氟尿嘧啶为原料，经羰基保护、烷基化、叠氮化反应制得1-(3-叠氮丙基)-5-氟尿嘧啶，最后再利用药物拼合原理将其与不同含有端炔取代的4-苯胺喹唑啉类化合物或厄洛替尼通过Click反应合成了7个5-氟尿嘧啶与4-苯胺喹唑啉骨架的新型拼接产物，其结构通过1HNMR和HRMS确证。以厄洛替尼为阳性对照，采用MTT法初步评价目标化合物对人肝癌细胞HepG2、人非小细胞肺癌细胞A549、人宫颈癌细胞Hela、人乳腺癌细胞MCF-7、人肺腺癌耐顺铂株细胞A549/DDP的抑制作用，同时采用ELISA法检测目标产物对EGFR的抑制能力。结果显示，1-(3-(4-(((4-((4-碘苯基)氨基)-7-甲氧基喹唑啉-6-基)氧)甲基)-1H-1,2,3-三唑-1-基)丙基)-5-氟尿嘧啶-2,4(1H,3H)-二酮对HepG2、A549、A549/DDP细胞的抑制作用分别是阳性对照厄洛替尼的6.5倍、1.8倍、2.8倍，对Hela、MCF-7细胞的IC50也分别达到了（0.95 ± 0.33）μmol/L，（1.26 ± 0.55） μmol/L。同时，该化合物在0.01、0.1 μmol/L对EGFR的抑制作用弱于阳性对照厄洛替尼，提示该化合物并非只通过作用于EGFR产生抗肿瘤作用，可能还存在的其他作用途径，值得进一步研究。
关键词：5-氟尿嘧啶；喹唑啉；Click反应；抗肿瘤；表皮生长因子
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis and Antitumor Activity of 5-Fluorouracil and 4-Anilinoquinazoline Skeleton Based on Click Approach LIANG Guang-ping1, YANG Jie1, LIANG Guang-yan2, WANG Dao-ping2, YANG Jun*1 (1. Department of Pharmacy, Zunyi Medical and Pharmaceutical College, Zunyi 563006, China; 2. The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guiyang 550014, China), Huaxue Shiji, 2022, 44（9）
Abstract：Hydantoin is a class of five-membered heterocyclic compound with four functional points, showing various amazing biological and pharmacological activities. This small and rigid backbone could effectively act on various pharmacological targets. Several clinically important medicines such as phenytoin (antiepileptic), azimilide (antiarrhythmic) and nilutamide (antiandrogen) are based upon this characteristic staple scaffold. RU58841(IUPAC name: 4‐[3‐(4‐hydroxybutyl)‐4,4‐dimethyl‐2,5‐dioxoimidazolidin‐1‐yl]‐2‐(trifluoromethyl)benz onitrile) was found active against baldness with little evidence of toxicity, showing a good promise as a topically new active non-steroidal antiandrogen. In this work, we develop a new alternative strategy for synthesis of RU58841 by using 4-amino-2-(trifluoromethyl) benzonitrile as a raw material in four steps including the preparation of isocyanate, [3+2] cycloaddition, N-alkylation and deprotection with over-all yield of 40%. Compare to traditional methods for preparation of RU58841, the strategy in this work is more convenient and safer.
Key words：5-fluorouracil; quinazoline; Click reaction; antitumor; EGFR
引用本文：梁光平, 杨杰, 梁光焰, 等. 基于Click反应的5-氟尿嘧啶与4-苯胺喹唑啉骨架的拼接合成及其抗肿瘤活性评价[J]. 化学试剂, 2022, 44(9):1272-1279.
基于靛红酸酐-苯并噻唑的Hg2+可视化荧光探针的合成及性能研究
赵小丽，吴林利，杨迪，冷艳丽，李小红*，蔡小华*
（贵州民族大学 化学工程学院，贵州 贵阳 550025）
摘要：Hg2+由于易生物积累和高毒性的特点，会对人体健康和环境带来严重的危害，因此开发Hg2+简便、快速、选择性好、灵敏度高的检测方法非常重要。通过一步水热法合成2-氨基-N-(苯并噻唑基)苯甲酰胺，可在含水体系（V(DMSO)：V(H2O) = 1:1）中快速检测Hg2+，Hg2+加入后，荧光显著猝灭。且检测时不受Ca2+、Hg2+、Mn2+、Cd2+、Co2+、Mg2+、Al3+、Ag+、Zn2+、Ni2+、Fe3+、Cu2+和Pb2+的干扰，具有良好的专一选择性。同时，研究了该荧光探针检测Hg2+的试纸实验，发现在荧光探针溶液浓度为2×10-4 mol/L时，可以明显的检测出Hg2+。表明该探针对食品和环境中Hg2+的检测中具有潜在的应用前景。
关键词：荧光探针；Hg2+；选择性；靛红酸酐；2-氨基苯并噻唑
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2022）
Study and Synthesis of Hg2+ Visible Fluorescent Probe Based on Indigo Anhydride-benzothiazole ZHAO Xiao-li, WU Lin-li, YANG Di, LENG Yan-li, LI Xiao-hong*, CAI Xiao-hua* (Guizhou Minzu University, Guiyang 550025), HuaxueShiji, 2022
Abstract: Mercury (Hg2+) in aquatic ecosystems is always an important issue because it is one of the most prevalent and dangerous pollutants, with the character of easy bioaccumulation and high toxicity.So it is very important to develop a simple, rapid, selective and sensitive detection method for Hg2+.In this study, we reported a novel fluorescent probe synthesized by one-step hydrothermal method for visual detection of Hg2+ based on a chromogenic reaction under ultraviolet light. It can quickly detect Hg2+ in aqueous system (V(DMSO):V(H2O) = 1:1)with the significant quenching of fluorescence intensity. In addition, the compound 1 can be used to effectively and selectively detect Hg2+ions over other metal ions with a good linear response. At the same time, the test paper experiment of detecting Hg2+ with this fluorescent probe was studied, and it was found that when the concentration of fluorescent probe solution was 2×10-4 mol/L, Hg2+ could be detected obviously.It shows that the probe has a potential application prospect in the detection of Hg2+ in food and environment.
Key words: fluorescence probe; Hg2+; selectivity; indigo anhydride; 2-aminobenzothiazole
引用本文：赵小丽,吴林利,杨迪,等.基于靛红酸酐-苯并噻唑的Hg2+可视化荧光探针的合成及性能研究[J].化学试剂, 2022,44(9): 1280-1286.
氨基修饰的N-O功能化金属有机框架材料的发光性能
张文谦*，牛亚杰，曹铎
（信阳农林学院 制药工程学院，河南 信阳 464000）
摘要：荧光类的金属有机框架（MOFs）因其突出的光学特性、永久孔隙率、可调控的结构和相对较长的发射波长，成为一种具有广阔应用前景的新型传感材料。采用协同策略，将轴手性2,2'-联吡啶-3,3'-二羧酸-1,1'-二氧（H2dpdcdo）含氧配体和氨基修饰的N2-(吡啶-2-基)吡啶-2,6-二胺（pda）含氮配体，通过扩散法与Zn(OAc)2·2H2O金属盐合成了一种新型荧光MOF材料{[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n。通过单晶X射线衍射（SCXRD）、粉末X射线衍射（PXRD）、红外光谱（IR）、元素分析（EA）、热重分析（TGA）和荧光光谱对MOF {[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n进行了表征。材料{[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n中R和S-dpdcdo配体连接Zn1与pda分别产生一维左手链和右手链，两种手性链之间通过氢键作用和π-π堆积作用形成了三维外消旋结构。固态荧光测试显示，MOF {[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n相比于配体，发射峰出现了大幅度红移，在523 nm处有一强发射峰，在紫外灯照射下发出明显的黄绿色荧光。离子识别实验表明MOF 材料{[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n是一种检测MnO4-离子的良好荧光探针。
关键词：荧光金属有机框架；荧光传感；荧光淬灭；离子识别
中图分类号：O61 文献标识码：A 文章编号：0258-3283（2022）
Fluorescent Properties of Amino-Decorated N-Oxide Functional Metal-Organic Framework ZHANG Wen-qian*, NIU Ya-jie, CAO Duo. (College of Pharmaceutical Engineering, Xinyang Agricultural and Forestry University, Xinyang 464000, China), Huaxue Shiji, 2022,
Abstract：Fluorescent metal-organic frameworks (MOFs) have become a new sensing material with broad application prospects because of their outstanding optical properties, permanent porosity, adjustable structures and relatively long emission wavelength. A novel fluorescent MOF, {[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n, was synthesized by synergistical combination of diffusion method with axial chirality 2,2'-bipyridine-3,3'-dicarboxylic acid-1,1'-dioxygen (H2dpdcdo) as oxygenated ligand, amino-decorated N2-(pyridin-2-yl) pyridine-2,6-diamine (pda) as nitrogenous ligand, and Zn(OAc)2·2H2O as metal salt. The obtained MOF was characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis (TGA) and fluorescent spectroscopy. In MOF {[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n, R and S-dpdcdo ligands connect with Zn1 and pda to produce one-dimensional left-handed chains and right-handed chains, respectively. And then, they are extended by hydrogen bonding and π-π stacking interactions to form a three-dimensional racemic structure. The solid-state fluorescence tests show that compared with the ligands, the emission peak of as-prepared MOF exhibits a significant red shift at 523 nm, which corresponds to obvious yellow-green fluorescence under the irradiation of UV lamp. Anion recognition tests demonstrate that MOF {[Zn(dpdcdo)(pda)]·H2O·0.5DMF}n is an efficient fluorescent probe for detection of MnO4- ion.
Key words：fluorescent metal-organic framework; fluorescence sensing; fluorescence quenching; ion recognition
引用本文：张文谦, 牛亚杰, 曹铎. 氨基修饰的N-O功能化金属有机框架材料的发光性能[J]. 化学试剂, 2022,44（9）：1287-1293.
一个单核钴(Ⅱ)超分子配合物的合成、晶体结构及类Fenton催化性质研究
张倩*a，叶英杰a，于琼燕b，陈垒a
（河南工程学院 a.化工与印染工程学院，b.材料工程学院，河南 郑州 450007）
摘要：合成得到了一个配体1,3-二羧甲基苯并咪唑，将其与Co(Ac)2·4H2O在水溶液中反应得到了一个新的单核钴(II)配合物，并通过X-射线单晶衍射和元素分析表征了其晶体结构。配合物为一个金属中心与2个配体和4个水分子形成的单核结构，单核结构之间再通过O—H···H氢键及π···π堆积作用组装成三维超分子网络结构。并测试了此配合物的物相纯度、热稳定性质和作为非均相类Fenton试剂的催化性质，测试结果表明，配合物显示了良好的物相纯度，对甲基橙溶液可以达到86.0%的降解率，显示了良好的类Fenton催化性质，表明其是一种潜在的催化降解有机污染物的材料。
关键词：钴(Ⅱ)超分子配合物；晶体工程；苯并咪唑二羧酸；类Fenton试剂；甲基橙降解
中图分类号：O614 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis, crystal structure and Fenton-like catalytic property of a Cobalt(II) mononuclear supramolecular complex ZHANG Qian*1, YE Ying-jie1, YU Qiong-yan2 , CHEN Lei1 (1.College of Chemical and Printing-dyeing Engineering, Henan University of Engineering, Zhengzhou 450007, Henan; College of Materials Engineering, Henan University of Engineering, Zhengzhou 450007, Henan), Huaxue Shiji, 2022, 44(9), ～
Abstract: Mercury (Hg2+) in aquatic ecosystems is always an important issue because it is one of the most prevalent and dangerous pollutants, with the character of easy bioaccumulation and high toxicity. So it is very important to develop simple, rapid, selective and sensitive detection methods for Hg2+. In this study, we reported a novel fluorescent probe synthesized by one-step hydrothermal method for visual detection of Hg2+ based on a chromogenic reaction under ultraviolet light. Hg2+ can be quickly detected in aqueous system (V(DMSO) : V(H2O) = 1:1) on the basis of the significant quenching of fluorescence intensity. In addition, the compound 1 can be used to effectively and selectively detect Hg2+ ions over other metal ions (Ca2+、Hg2+、Mn2+、Cd2+、Co2+、Mg2+、Al3+、Ag+、Zn2+、Ni2+、Fe3+、Cu2+ and Pb2) with a good linear response. Furthermore, the test paper experiment of detecting Hg2+ by this fluorescent probe was studied, and it was found that when the concentration of fluorescent probe solution was 2×10-4 mol/L, Hg2+ could be distinguished obviously. Such probe shows a good potential for the detection of Hg2+ in food and environment.
Key words: Co(II) supramolecular complex; crystal engineering; benzimidazolyl dicarboxylic acid; Fenton-like agent; MO degradation
引用本文：张倩，叶英杰，于琼燕，等. 一个单核钴(Ⅱ)超分子配合物的合成、晶体结构及类Fenton催化性质研究[J]. 化学试剂,2022,44(9): 1294-1298。
脱脂油茶籽粕多糖的提取及抗氧化活性研究
林莉*1，石庆楠2，周敏1，杨卫林3，龙开伟3，罗丽君1
（1. 凯里学院 大健康学院，贵州 凯里 556001；2. 黔东南州食品药品检验检测中心，贵州 凯里 556000；3. 贵州绿色农业开发有限公司，贵州 锦屏 556704）
摘要：研究水提醇沉法提取多糖的工艺并测定其体外抗氧化活性，以期为提高油茶副产物资源的利用率提供理论依据。以脱脂油茶籽粕为原料，采用水提醇沉法在单因素试验基础上结合响应面法对多糖提取工艺优化，并通过测定DPPH自由基、O2-自由基、·OH自由基分析其体外抗氧化活性。脱脂油茶籽粕多糖提取的最佳工艺参数为V（料）∶V（液）=1∶30 （g/mL）、提取温度80 ℃、提取时间50 min，在此工艺参数下脱脂油茶籽粕多糖提取率为49.25%，RSD为0.24%；清除DPPH自由基、O2-自由基、·OH自由基的半抑制浓度（IC50）分别为1.67、1.44、1.94 mg/mL。响应面试验建立的优化模型对脱脂油茶籽粕多糖提取率分析可靠且所得多糖具有一定的体外抗氧化效果。
关键词：脱脂油茶籽粕；多糖；响应面；提取；抗氧化活性
中图分类号：TS202.1 文献标识码：A 文章编号：0258-3283（2022）--
Study on extraction and antioxidant activity of polysaccharide from degreased camellia LIN Li*1, SHI Qing-nan2, ZHOU Min1, YANG Wei-lin3, LONG Kai-wei3, LUO Li-jun1（1.School of Life and Health Science, Kaili college, Kaili 556001, China; 2. Qiandongnan Food and Drug Inspection and Testing Center, Kaili 556001, China; 3. Guizhou Green Agriculture Development Co. Ltd, Jinpin 556704, China）, Huaxue Shiji, 2022, 44(9), ～
Abstract: In the purpose of providing theoretical basis for improving the utilization rate of camellia byproduct resources, we study the extraction technology of polysaccharide by water extraction and alcohol precipitation method, and evaluate its antioxidant activity in vitro. By employing degreased camellia as a raw material, and optimizing the extraction process of polysaccharide through water extraction and alcohol precipitation method on the basis of single factor test and response surface methodology, the antioxidant activity of polysaccharides was then evaluated by DPPH, O2- and ·OH radicals. The optimal extraction conditions were demonstrated to be solid-liquid ratio of 1 : 30 （g/mL）, temperature of 80 ℃ and time of 50 min. Under these conditions, the extraction rate and RSD of polysaccharides was determined to be 46.12% and 0.24%, respectively. Meanwhile, the scavenging concentrations (IC50) for DPPH, O2- and ·OH radicals were 1.67, 1.44 and 1.94 mg/mL. The optimized model established by response surface test was reliable for the extraction rate analysis of polysaccharides from defatted camellia, and the obtained polysaccharides showed good antioxidant activity in vitro.
Key words: Degreased camellia;polysaccharide;responsesurface;extraction;antioxidantactivity
引用本文：林莉，石庆楠，周敏，等. 脱脂油茶籽粕多糖的提取及抗氧化活性研究[J]. 化学试剂，2022，44(9): 1299-1305。
铝离子电池正极材料的研究进展
谭斌1，罗文斌*2，晁自胜*2
（1.湖南铁道职业技术学院，湖南 株洲 412001；
2.长沙理工大学 材料科学与工程学院，湖南 长沙 410114）
摘要：Al价格低廉且储量在地壳中储量较为丰富，体积比容量最高，电化学当量和质量比容量仅分别略高于和低于Li，因此，铝离子电池具有非常广阔的发展前景。然而，铝离子电池正极材料尚存在着一些问题：循环稳定性强但放电比容量低或放电比容量高但容量衰减严重。此外，充放电反应机理上也存在分歧，这些问题的存在限制了高能量密度铝离子电池的进一步发展。结合前人相关研究，总结了铝离子电池正极材料的研究现状和优化方法，并对相关问题进行了分析与展望。
关键词：铝离子电池；正极材料；金属硫化物；金属氧化物；碳材料
中图分类号：TM912 文章标识码：A 文章编号：0258-3283（2022）
Research Progress of Cathode Materials for Aluminum Ion Batteries TAN Bin1, LUO Wen-bin*2, CHAO Zi-sheng*2 (1. Hunan Railway Professional Technology College, Zhuzhou 412001, China; 2. College of Materials Science and Engineering，Changsha University of Science and Technology, Changsha 410114, China), Huaxue Shiji, 2022,44（9）
Abstract: Due to its low price, richest reserve in the crust and highest volume specific capacity of Al, along with its electrochemical equivalent and mass specific capacity are only slightly higher and lower than Li, therefore aluminum-ion batteries (AIBs) have a very broad application potential. Nevertheless, there are still some problems in the cathode materials of aluminum-ion batteries, such as strong cycle stability but low discharge capacity, or high discharge capacity rather than serious capacity fading. In addition, there are controversies in the charge-discharge reaction mechanisms, limiting the further development of high energy density aluminum ion batteries. In this review, the research status of cathode materials was summarized based on previous research and theories, and the current related problems and perspectives were discussed as well.
Key words: aluminum ion batteries; cathode materials; metal sulfide; metal oxide; carbon material
引用本文：谭斌，罗文斌，晁自胜. 铝离子电池正极材料的研究进展[J].化学试剂，2022,44（9）:1306-1313.
虚拟模板分子印迹材料固相萃取磺胺类抗生素
王艺晓1,4,孙宏宵1,2a，王莉燕1,4，纪灵*3，孙大妮1,2c，刘惠涛2c，宋志花2b，李金花*1,4
中国科学院烟台海岸带研究所 山东省海岸带环境工程技术研究中心 中国科学院海岸带环境过程与生态修复重点实验室 山东省海岸带环境过程重点实验室，山东 烟台 264003；2. 烟台大学 a. 环境与材料工程学院，b.药学院 分子药理和药物评价教育部重点实验室 新型制剂与生物技术药物研究山东省高校协同创新中心，c.化学化工学院，山东 烟台 264005；3. 国家海洋局烟台海洋环境监测中心站，山东 烟台 264006；4. 中国科学院大学，北京 100049）
摘要：以磺胺苯（SZ）为虚拟模板，一步沉淀聚合制备虚拟模板分子印迹聚合物（DMIPs）材料，用于同时分散固相萃取（DSPE）水样中4种磺胺类抗生素（SAs），结合HPLC-UV进行测定。对DMIPs进行表征与吸附性能评价，其对4种SAs的最大吸附量为21.97～30.24 mg/g，印迹因子均大于2.1。优化DMIPs用量、萃取时间、样品溶液pH等，确定最佳DSPE和HPLC条件。在湖水、海水、自来水中评价方法的分析性能，得到3种水样中的线性范围为1～200 μg/L、检出限0.27～0.64 μg/L和定量限0.99～2.14 μg/L。基质效应结果（ME%≤6%）表明DMIPs-DSPE有效消除了复杂基质干扰、提高了检测准确度。4种SAs在3中水样中的回收率为93.8%～102.6%，相对标准偏差（RSD）为2.6%～7.0%。该DMIPs-DSPE-HPLC-UV法简单快速、灵敏准确，适于复杂样品中痕量SAs多残留分析。
关键词：磺胺类抗生素；分子印迹聚合物；虚拟模板；固相萃取；环境水样; 高效液相色谱
中图分类号：O615.4 文献标识码：A 文章编号：0258-3283（2022）
Solid-phase Extraction of Sulfonamides Antibiotics by Using Dummy Template Based Molecularly Imprinted Materials WANG Yi-xiao1,4, SUN Hong-xiao1,2a, WANG Li-yan1,4, JI Ling*3, SUN Da-ni12c, LIU Hui-tao2c, SONG Zhi-hua2b, LI Jin-hua*1,4（1.CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Shandong Key Laboratory of Coastal Environmental Processes, Shandong Research Center for Coastal Environmental Engineering and Technology, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China; 2. a. School of Environmental and Material Engineering;b.School of Pharmacy, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Key Laboratory of Molecular Pharmacology and Drug Evaluation (Yantai University), Ministry of Education,c. College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China; 3. Yantai Oceanic Environmental Monitoring Central Station, State Oceanic Administration, Yantai 264006, China; 4. University of Chinese Academy of Sciences, Beijing 100049, China)
Abstract：In this work, dummy template molecularly imprinted polymers (DMIPs) were prepared by one-step precipitation polymerization using sulfameobenzene (SZ) as a dummy template, and applied for the simultaneous dispersion of four typical SAs in solid-phase extraction (DSPE), followed by high performance liquid chromatography-UV (HPLC-UV) determination. The DMIPs was characterized by several techniques, such as SEM and FT-IR, and its static/dynamic adsorption and selectivity were all evaluated by using adsorption models. The maxima adsorption capacities of sulfamonomethoxine (SMM), sulfachloropyridazine (SFZ), sulfamethoxazole (SMX) and sulfadimethoxine (SDM) were 30.24, 28.61, 21.97 and 22.37 mg/g, respectively, and the imprinting factors were all greater than 2.1. The factors affecting the extraction efficiency of DMIPs-DSPE, mainly including dosage of DMIPs, extraction time, pH of sample solution, volume of desorption and time of desorption were systematically optimized. Under the optimal conditions, the DMIPs-DSPE-HPLC-UV methods attained good linearity in the range of 1～200 μg/L with correlation coefficients ≥0.9995, and the limits of detection (LODs) were between 0.27～0.64 μg/L and the limits of quantification (LOQs) were 0.99～2.14 μg/L in lake water, seawater and tap water samples. The precision of the method was excellent, for example, the intraday precision (relative standard deviation, RSD) of retention time and peak area of the four SAs were 0.07%～0.12% and 0.53%～1.13%, respectively, and the interday precision was 0.23%～0.28% and 0.95%～1.33%, respectively. The matrix effect (ME) of the method was investigated to be ME ≤ 6% in the above three water samples, indicating that the developed method can effectively eliminate the interference of complex matrices. The recoveries of four SAs in lake water, seawater, tap water were 93.8%～99.8%, 94.8%～100.1% and 95.6%～102.6%, respectively, with RSD of 2.6%～7.0%, 2.8%～5.4% and 2.8%～5.2%. The simple, rapid, sensitive and accurate DMIPs-DSPE-HPLC-UV method proved applicable for multiresidue analysis of SAs in complicated samples.
Key words：sulfonamides antibiotics;molecularly imprinted polymers;dummy template;solid-phase extraction;environmental water samples;high performance liquid chromatography
引用本文：王艺晓,孙宏宵，王莉燕，等.虚拟模板分子印迹材料固相萃取磺胺类抗生素[J].化学试剂，2022，44（9）：1314-1324.
汞离子荧光探针的研究进展
张人杰，史纪福，王雪，冯贞，刘姝菂*
（烟台大学 化学化工学院，山东 烟台 264005）
摘要：汞是一种具有生物积累性的重金属元素，与一系列疾病的发生发展有密切联系。为了实现汞离子的实时原位可视化检测，近年来检测汞离子的有机小分子荧光探针发展迅速并有相关综述报道，但对于高分子荧光材料检测汞离子的研究报道极少。与其他汞离子研究进展综述不同之处在于以汞离子的检测机理为出发点，分别从设计原理、选择性、灵敏度和实用性角度综述，简要介绍了近年来有机小分子探针的设计策略，并详细介绍了基于功能高分子荧光材料检测汞离子的研究进展，将其检测策略归纳为配位型、反应型及两者结合型三类，以期为汞离子荧光探针的设计及发展提出新的研究思路。
关键词：荧光探针；汞离子；高分子荧光材料；检测机理；配位作用
中图分类号：O614.24 文献标识码：A 文章编号：0258-3283（2022）
Recent Progress in Mercury Ions Fluorescent Probes ZHANG Ren-jie, SHI Ji-fu, WANG Xue, FENG Zhen, LIU Shudi* (College of Chemistry and Chemical Engneering, Yantai University, Yantai 264005, China) , Huaxue Shiji，2022，44 (9)，00 ~ 00
Abstract：Mercury is a heavy metal element closely related to the occurrence and development of a series of diseases on account of its bioaccumulation. In order to realize the in situ and real-time visual detection of mercury ions, small organic molecules based fluorescent probes for mercury ions have been developed rapidly in recent years and these related works have been summarized and reported as review papers, but the mercury ion probes fabricated using polymer fluorescent materials have been rare reviewed. The difference between this review and others is that the research progress of small organic molecule based mercury ions fluorescent probes was first briefly introduced and then highlights the advances in mercury ions detection using functional fluorescent polymer materials in recent years, including design principle, selectivity, sensitivity and practicality. The detection strategies were classified into three types, including coordination type, reaction-based type and combination type based on aspects of response mechanism strategy. This review would be helpful to design and develop ideal fluorescent probes for mercury ions detection.
Key words：fluorescent probe; mercury ions; polymer fluorescent materials; detection mechanism; coordination
引用本文：张人杰，史纪福，王雪，等.汞离子荧光探针的研究进展[J]. 化学试剂，2022，44(9): 1325-1333。
喹诺酮类抗生素的分子印迹电化学传感检测
温宇浩1,3，孙大妮2,3，张悦3，周娜3，刘惠涛2，李金花*1,3，庄旭明*2
哈尔滨工业大学（威海） 海洋科学与技术学院，山东 威海 264209；2.烟台大学 化学化工学院，山东 烟台 264005；3.中国科学院烟台海岸带研究所 山东省海岸带环境工程技术研究中心 中国科学院海岸带环境过程与生态修复重点实验室 山东省海岸带环境过程重点实验室，山东 烟台 264003)
摘要：喹诺酮类抗生素（QNs）残留极大危害生物体和环境，其含量低、种类多、基质复杂，通常需要进行样品前处理结合色谱/质谱分析以实现灵敏检测。分子印迹聚合物（MIPs）是具有与模板分子在形状、大小及官能团完全匹配的特异性识别位点的高分子聚合物，能选择性识别和富集目标分析物并消除干扰。电化学传感器具有高灵敏度、高选择性、响应时间短等优点，将分子印迹技术应用其中，得到的分子印迹电化学传感器（MIEC）具备了二者的优点。综述了MIEC的构建原理，主要包括电流传感器和电位传感器。此外，重点介绍了MIEC在工业生产和实际生活中对QNs的检测，包括恩诺沙星、氧氟沙星等。最后，提出了MIEC在QNs快速检测中面临的挑战和发展前景。
关键词：喹诺酮类抗生素；分子印迹聚合物；电化学传感器；构建原理；快速检测
中图分类号：O657.1 文献标识码：A 文章编号：
Molecular Imprinting based Electrochemical Detection of Quinolones Antibiotics WEN Yu-hao1,3, SUN Da-ni2,3, ZHANG Yue3, ZHOU Na3, LIU Hui-tao2, LI Jin-hua*1,3, ZHUANG Xu-ming*2 (1. School of Marine Science and Technology, Harbin Institute of Technology (Weihai), Weihai 264209, China; 2. College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China; 3. CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Shandong Key Laboratory of Coastal Environmental Processes, Shandong Research Center for Coastal Environmental Engineering and Technology, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China)
Abstract: The residues of quinolones (QNs) antibiotics are extremely harmful to organisms and the environment. QNs are low in content and diverse in species, and present in complex matrices. Usually, sample pretreatment combined with chromatographic/mass spectrometry analysis is required to achieve sensitive detection. Molecularly imprinted polymers (MIPs) are high molecular polymers with specific recognition sites that exactly match template molecules in shape, size and functional groups, which can selectively recognize and enrich target analytes and eliminate interference. Electrochemical sensors have the advantages of high sensitivity and selectivity, and short response time. Molecularly imprinted electrochemical sensors (MIES) obtained by applying molecular imprinting technology have the advantages of both MIPs and electrochemical sensors. In this Review, we summarize the construction principles of MIEC, mainly including current sensors and potential sensors. The detection of QNs (enrofloxacin, ofloxacin, etc.) in industrial production and real life by MIES is then highlighted. Finally, the challenges and development prospects of MIEs in rapid detection of QNs are discussed.
Key words：quinolones antibiotics; molecularly imprinted polymers; electrochemical sensors; construction mechanism; rapid detection
引用本文：温宇浩，孙大妮，张悦，等.喹诺酮类抗生素的分子印迹电化学传感检测[J].化学试剂，2022，44（9）：1334-1341.
环境新污染物风险防范与化学品环境管理
时巧翠1，傅佳宇2，陈金媛*2，周宇畅1
（1.浙江警察学院 浙江省毒品防控技术研究重点实验室，浙江 杭州 310053；
2. 浙江工业大学 环境学院，浙江 杭州 310014）
摘要：随着各类化学品的大量使用，环境内分泌干扰物、新型持久性有机污染物、微塑料和抗生素等新污染物对生态环境和人体健康的危害正逐步显现并日趋严重。如何进一步完善我国环境新污染物的风险防范体系，是我国生态环境治理面临的重要问题。化学品环境管理是防范环境新污染物风险的重要环节。通过查阅文献资料梳理了我国环境新污染物风险防范和化学品管理的政策法规及相关规定，在此基础上，结合当前存在的问题，从制度建设、体制机制、监测评估及科学研究等方面提出了建议。
关键词：环境内分泌干扰物；新型持久性有机污染物；微塑料；抗生素；风险防范；化学品环境管理
中图分类号：X327 文献标识码：A 文章编号：0258-3283（2022）
Risk Prevention of Emerging Pollutants and Environmental Management of Chemicals SHI Qiao-cui 1, FU Jia-yu 2, CHEN Jin-yuan *2, ZHOU Yu-chang1 (1.Laboratory of Drug Prevention and Control Technology of Zhejiang Province, Zhejiang Police College Hangzhou 310053，China; 2.College of Environment, Zhejiang University of Technology, Hangzhou 310014,China) , Huaxue Shiji，2022，44 (9)
Abstract: With the extensive use of various chemicals, the harm of some new emerging pollutants such as environmental endocrine disruptors, new persistent organic pollutions, microplastics and antibiotics to Chinese residents, ecology and environment is gradually appearing, and it is becoming more and more serious. How to further improve the risk prevention system of China’s emerging pollutants is an important issue facing China’s ecological environment governance. Synthetic chemicals and unintentionally released chemical substances constitute an important source of new emerging pollutants. Environmental management of chemicals is very imperative to risk prevention of emerging pollutants. This review summarizes the literatures on China’s policies, laws and related regulations of risk prevention of emerging pollutants and control of chemicals. And on this basis we put forward the system construction, system and mechanism, evaluation and monitoring, and scientific research suggestions.
Key words：environmental endocrine disruptors; new persistent organic pollutions; microplastics; antibiotics; risk prevention; environmental management of chemicals
引用本文：时巧翠，傅佳宇，陈金媛，等. 环境新污染物风险防范与化学品环境管理[J]. 化学试剂，2022，44( 9): 1342-1349。
分子印迹技术用于抗生素残留检测的研究进展
赵广丽1，张悦1，孙大妮2，周娜*2，韩铠营1，闫李霞3，于佳洛2，宋志花1，李桂生*1
（1. 烟台大学 药学院 分子药理和药物评价教育部重点实验室 新型制剂与生物技术药物研究山东省高效协同创新中心，山东 烟台 264005；2. 中国科学院烟台海岸带研究所 中国科学院海岸带环境过程与生态修复重点实验室，山东 烟台 264003；3. 山东省烟台第二中学，山东 烟台 264000）
摘要：模拟酶-底物或抗原-抗体特异性结合原理的分子印迹技术（MIT）在目标物识别和检测中应用广泛。MIT制备的分子印迹聚合物（MIPs）为吸附剂的分子印迹固相萃取（MISPE）和基于MIPs的传感分析均已广泛应用于抗生素的分析检测中。简要介绍了抗生素MIPs的几种新兴制备技术，包括表面印迹、纳米印迹、活性可控自由基聚合、多模板印迹、多功能单体印迹和虚拟模板印迹；然后，概述了基于MIPs的3种固相萃取（SPE）模式，即传统装柱固相萃取、磁固相萃取、分散固相萃取，以及基于MIPs传感器的基本原理。随后，重点综述了近5年MISPE和基于MIPs的电化学和荧光传感器用于环境和食品等样品中的各种抗生素残留检测的研究进展，包括磺胺类、喹诺酮类、四环素类等。最后，对抗生素MIPs的制备和应用进行了展望。
关键词：抗生素；印迹技术；分子印迹聚合物；固相萃取；传感器
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2022）
Research Advances of Molecular Imprinting Technology for the Detection of Antibiotics Residues ZHAO Guang-li1, ZHANG Yue1, SUN Da-ni2, ZHOU Na*2, HAN Kai-ying1, YAN Li-xia3, YU Jia-luo2, SONG Zhi-hua1, LI Gui-sheng*1 (1. Key Laboratory of Molecular Pharmacology and Drug Evaluation, Ministry of Education, Shandong Provincial High-efficiency Collaborative Innovation Center for Novel Formulations and Biotechnology Drug Research, School of Pharmacy, Yantai University, Yantai 264005, China; 2. CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China; 3. Yantai No.2 Middle School of Shandong Province, Yantai 264000, China), Huaxue Shiji, 2022,
Abstract: Molecular imprinting technology (MIT), which mimics the specific binding principle of enzyme-substrate or antigen-antibody, is widely used in target recognition and detection. Molecularly imprinted polymers (MIPs) based sensing assays and molecularly imprinted solid-phase extraction (MISPE) fabricated from MIPs (prepared by MIT) as adsorbents, have been widely applied in the detection of antibiotics. This review briefly introduces several emerging preparation techniques for antibiotics MIPs, including surface imprinting, nanoimprinting, living-controlled radical polymerization, multitemplate imprinting, multifunctional monomer imprinting, and dummy template imprinting. Solid-phase extraction (SPE) modes, namely traditional column-packed SPE, magnetic SPE, dispersive SPE, and the basic principle of MIPs based sensors are outlined. Subsequently, the recent 5-year application advances of MISPE and MIPs-based electrochemical and fluorescence sensors in the detection of various antibiotics residues, such as sulfonamides, quinolones and tetracyclines in environmental, food and other samples are highlighted. Finally, the preparation and application of antibiotics MIPs are prospected.
Key words：antibiotics; imprinting technology; molecularly imprinted polymers; solid-phase extraction; sensors
引用本文：赵广丽, 张悦, 孙大妮, 等. 分子印迹技术用于抗生素残留检测的研究进展[J]. 化学试剂, 2022, 44（9）：1350-1359.
分子印迹技术在中药研究中的应用进展
韩铠营，张悦，宋志花*，毕毅，杨刚强，李桂生*
（烟台大学 药学院 分子药理和药物评价教育部重点实验室 新型制剂与生物技术药物研究山东省高校协同创新中心，山东 烟台 264005）
摘要：目前，在中药现代化和国际化背景下，中药的相关研究也进入了发展快车道。中药研究面临化学成分多样、基质复杂、有效成分含量低等挑战，传统样品前处理方法由于所需时间长、选择性低等问题难以解决上述问题。分子印迹技术（Molecular Imprinting Technology，MIT）制备的分子印迹聚合物（Molecularly Imprinted Polymers，MIPs）凭借其高选择性已在中药研究领域大显身手，广泛用于中药中有效成分提取、有害成分分析、中药代谢研究等多个方面。总结了2017~2022年MIT在中药研究中的应用进展，展望了MIT在中药研究中的应用。
关键词：分子印迹；中药；富集；提取；检测；代谢产物
中图分类号：R932 文献标志码：A 文章编号：0258-3283（2022）
Recent Progress in Research on Traditional Chinese Medicine Based on Molecular Imprinting Technology HAN Kai-ying, ZHANG Yue, SONG Zhi-hua*, BI Yi, YANG Gang-qiang, LI Gui-sheng* (School of Pharmacy,Key Laboratory of Molecular Pharmacology and Drug Evaluation（Ministry of Education）, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Yantai University, Yantai 264005, China), Huaxue Shiji, 2022,
Abstract：At present, under the background of modernization and internationalization of traditional Chinese medicine (TCM), the related research of TCM has entered the fast track of development. TCM research is faced with the challenges of diverse chemical components, complex matrix and low content of active components, which are difficult to be solved by traditional sample pretreatment methods due to long waiting time and insufficient selectivity. With their high selectivity, molecularly imprinted polymers (MIPs) prepared by molecular imprinting technology (MIT) have been widely used in the field of TCM research. It is widely used in the extraction of active components, analysis of harmful components and metabolism of traditional Chinese medicine. In this review, the application progress of MIT in TCM from 2017 to 2022 was summarized, and the perspectives on this research field were finally discussed as well.
Key words: molecular imprinting technology; traditional Chinese medicine; ingredient enrichment; ingredient extraction; pesticide detection; metabolites
引用本文：韩铠营, 张悦, 宋志花, 等. 分子印迹技术在中药研究中的应用进展[J]. 化学试剂, 2022, 44（9）：1360-1367.
LC-MS方法分析皮肤表面鞘脂的组成
佟薇1，江芝婷2，胡坪1，章弘扬*1
(1. 华东理工大学 化学与分子工程学院 上海市功能性材料化学重点实验室，上海 200237；2. 巴斯夫新材料有限公司 个人护理品部，上海 200137)
摘要：鞘脂作为角质层中最丰富的脂质，在皮肤屏障中起到重要作用。通过建立一种基于超高效液相色谱-四极杆-飞行时间质谱（UPLC-Q-TOF-MS）的分析方法，利用自建数据库匹配和二级质谱结构解析，对女性皮肤表面的108个鞘脂进行了鉴定并归纳其碎裂机理，其中包括34个鞘氨醇碱、65个神经酰胺（Cer）、8个1-磷酸神经酰胺（CerP）和1个磷酰鞘脂（PN-Cer）。随后将该方法应用于青、中年女性前臂皮肤鞘脂的检测，结合多元变量统计分析，初步探索了皮肤老化的鞘脂代谢差异。结果表明，不同年龄女性皮肤的鞘脂轮廓表现出明显的分组趋势，并筛选得到43个差异性鞘脂标志物，这些标志物相对含量的变化可能与衰老皮肤细胞中酶活性的变化有关。本研究为皮肤鞘脂的全面分析提供了新方法，也对皮肤衰老机制的探索及相关抗衰老护肤品的研发，具有一定的理论指导意义。
关键词：皮肤表面鞘脂；UPLC-Q-TOF-MS；多元变量统计分析；皮肤老化；差异性标志物
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2022）
Identification of Sphingolipid Compositions in the Skin of Young and Middle-aged Women by LC-MS TONG Wei1, JIANG Zhi-ting2, HU Ping1, ZHANG Hong-yang*1 (1. Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. Personal Care Department, BASF New Materials Co., Ltd., Shanghai 200137, China), Huaxue Shiji, 2022, 44(9)
Abstract：Sphingolipids, as the most abundant lipids in the stratum corneum, play an important role in skin barrier. In this paper, an analytical method based on ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was established to analyze the sphingolipids in women skin surface. By using personal database matching and MS/MS structural analysis, 108 sphingolipids were identified in the skin of women, including 34 of sphingosine bases, 65 of ceramides (Cer), 8 of ceramide 1-phosphates (CerP), and 1 of phosphonosphingolipid (PN-Cer). After then, this method combined with multivariate statistical analysis was applied to detect the metabolic perturbations of sphingolipids associated with skin aging in the young and middle-aged women forearm. The results showed that the skin sphingolipid profiles of young and middle-aged women exhibiting an obvious grouping trend, and 43 of differentiated sphingolipid markers were screened, which might be related to the changes of enzyme activities in aging skin cells. This study could provide a new method for the comprehensive analysis of skin surface sphingolipids, and it also has certain theoretical guiding significance for the exploration of skin aging mechanism and the research and development of related anti-aging skin care products.
Key words：skin surface sphingolipids; UPLC-Q-TOF-MS; multivariate statistical analysis; skin aging; differential markers
引用本文：佟薇，江芝婷，胡坪，等. LC-MS方法分析皮肤表面鞘脂的组成[J]. 化学试剂, 2022, 44(9): 1368-1375。
稳定性同位素分析在毒品溯源中的应用研究进展
赵志东1,2,3，孟娇1，巩京慧1，王晓卉1，张显强*1
（1.贵州警察学院，贵州 贵阳 550005；2.中国科学院广州化学所，广东 广州 510650；3.中国科学院大学，北京 100000）
摘要：综述了稳定性同位素技术在毒品来源推断中的应用研究进展，包括大麻、可卡因、海洛因、甲基苯丙胺和MDMA。通过对不同来源地毒品样品的同位素数据以及不同合成路径和反应条件下反应物和产物的同位素特征进行收集整理并进行深入剖析和挖掘，可以建立毒品样品与种植地、合成路径、工艺和反应条件的联系，进而实现毒品种植地或产地的推断。稳定性同位素分析数据对于毒品溯源追踪具有借鉴意义和参考价值。
关键词：法庭科学；稳定性同位素；毒品；溯源；合成路径；种植地
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2022）--
Research progress on the application of stable isotope analysis in illegal drug traceability ZHAO Zhi-dong1,2,3, MENG Jiao1, GONG Jing-hui1, WANG Xiao-hui1, ZHANG Xian-qiang* 1 (1.Guizhou Police College, Guiyang 550005; 2.Guangzhou Institute of Chemistry, Chinese Academic of Science, Guangzhou 510650; 3.University of Chinese Academic of Science, Beijing 100000,China), Huaxue Shiji, 2022, 44（9）
Abstract: In this Review, we summarized the application progress of stable isotope technology in tracing the source of drugs, including marijuana, cocaine, heroin, methamphetamine and MDMA. Links of growth location, along with synthetic routes, processes and reaction conditions of drug samples were established by collecting and sorting out. The obtained isotopic data of drug samples from different origins, the isotopic characteristics of reactants and products under different synthetic routes and reaction conditions, was then thoroughly analyzed and studied to infer the corresponding relation between the drugs and their places of origin (or growth location). Such analysis data of stable isotopes is significant for tracing the sources of drugs.
Key words: forensic science; stable isotopes; drugs; traceability; synthetic pathways; place of origin
引用本文：赵志东，孟娇，巩京慧，等. 稳定性同位素分析在毒品溯源中的应用研究进展[J]. 化学试剂,2022,44(9)：1376-1384.
多环芳烃类标准物质使用的稳定性评价
马宇熙1,2，张莹2，房苗2，阿力腾巴特2，孙向涛*2
（1. 新疆医科大学 新疆特殊环境与健康研究重点实验室，新疆 乌鲁木齐 830054
2. 乌鲁木齐市疾病预防控制中心，新疆 乌鲁木齐 830026）
摘要：为了对以不同溶剂为介质的多环芳烃混合标准溶液储存的稳定性进行了考察，选取200 mg·L-116种多环芳烃混合标准溶液，分别用乙腈和50%的乙腈配制成20 mg·L-1的中间液，在不同温度（-18 ℃、4 ℃）下避光储存、并于第7、15、30、60 d时用高效液相色谱对其特性量值进行测量。结果表明，标准溶液的特性量值在第一周就迅速衰减，7 ~ 30 d成直线下降趋势，且4 ℃比-18 ℃的衰减现象更明显，30 ~ 60 d时呈现负增长现象，说明溶剂蒸发逃逸是引起溶质浓缩导致量值增大的重要原因。多环芳烃类的混合标准溶液经开封稀释后不推荐重复使用，建议现用现配。
关键词：多环芳烃；标准物质；混合标准溶液；稳定性；评价；
中图分类号：O652.3 文献标志码：A 文章编号：0258-3283（2022）
Stability Evaluation for the Application of Polycyclic Aromatic Hydrocarbon Standards MA Yu-xi1,2, Zhang Ying2, FANG Miao2, ALITENGBATE2, SUN Xiang-tao*2 (1. Xinjiang Medical University Key Laboratory of Special Environment and Health Research in Xinjiang, Urumqi 830054, China; 2. Urumqi Centre for Disease Control and Prevention, Urumqi 830026, China), Huaxue Shiji, 2022,
Abstract: In order to investigate the storage stability of polycyclic aromatic hydrocarbons (PAHs) mixture standards with other different solvents, 16 kinds of PAHs (200 mg/L) mixture standards were selected as models to prepare intermediates (20 mg/L) by using acetonitrile and 50% acetonitrile, respectively. The obtained intermediates were stored at different temperatures (-18, 4℃) under dark condition, their characteristic values were subsequently monitored by high performance liquid chromatography on day 7, 15, 30 and 60. The results show that the characteristic values of standards decrease rapidly in the first week, and plummets from 7 to 30 days. Such attenuation phenomenon is more obvious at 4℃ than -18℃, and the negative growth phenomenon occurs from 30 to 60 days, suggesting the evaporation and escape of the solvent play important factor on inducing the concentration of the solute and thus increasing the characteristic values. Therefore, it will not be recommended to reuse the PAHs mixture standards once opened and diluted.
Key words: polycyclic aromatic hydrocarbons (PAHs); reference materials；mixture standards; stability；evaluation；
引用本文：马宇熙, 张莹, 房苗, 等. 多环芳烃类标准物质使用的稳定性评价[J]. 化学试剂, 2022, 44（9）：1385-1392.
抗癌药艾乐替尼关键中间体的合成工艺改进
田岩1,2，吴芳珍*1，黄一波1，张奉志3，张万妹1，苏怡1
(1.常州工程职业技术学院 检验检测认证学院，江苏 常州 230031；2.东华大学 化学化工与生物工程学院，上海 201620；3.枣庄市润安制药新材料有限公司，山东 枣庄 277101)
摘要：对艾乐替尼（Alectinib）关键中间体2-(4-乙基-3-碘苯基)-2-甲基丙酸的合成工艺进行了改进。以廉价易得的2-甲基-2-苯基丙酸为原料，通过缩合、傅克、还原、水解、碘代等反应得到的目标产物，经HPLC测定目标化合物的纯度为99.1%，整个合成路线中无需使用昂贵金属催化剂，反应条件温和，易于控制，并且可以以克级规模对中间体进行中试生产，总合成收率高达58%。改进后的工艺操作简单、成本低廉、易于工业化放大，为艾乐替尼关键中间体的合成提供了一种新的、高效的制备方法。
关键词：艾乐替尼；缩合；还原；碘代；合成工艺
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis Improvement of Key Intermediates of Anticancer Drug Alectinib TIAN Yan1,2, WU Fang-zhen*1, HUANG Yi-bo1, ZHANG Feng-zhi3, ZHANG Wan-mei1, SU Yi1 (1. Inspection and Testing Certification Institute, Changzhou Vocational Institute of Engineering, Changzhou 213164, China; 2. College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China；3. Zaozhuang Run'an Pharmaceutical New Material Co., Ltd., Zaozhuang, Shandong 277101), Huaxue Shiji, 2022, 44(9), ～
Abstract: In this study, the synthesis of 2-(4-ethyl-3-iodophenyl)-2-methylpropanoic acid, a key intermediate of Alectinib, was improved. Using cheap and easily available 2-methyl-2-phenylpropionic acid as a raw material, the target product is obtained by condensation, Friedel-Crafts, reduction, hydrolysis, iodination and other reactions, and purity of compound is determined to be 99.1% by HPLC. This entire synthesis route does not require expensive metal catalysts, the reaction conditions are mild and easy to control, and the intermediate can be produced on a gram scale in a pilot, with a total synthesis yield of up to 58%. The improved process has the advantages of simple operation, low cost and easy industrial scale-up, and provides a new and efficient preparation method for the synthesis of key intermediates of Alectinib.
Key words：alectinib; condensation; reduction; iodine; synthesis
引用本文：田岩，吴芳珍，黄一波，等. 抗癌药艾乐替尼关键中间体的合成工艺改进[J]. 化学试剂,2022,44(9): 1393-1397。
乙内酰脲衍生物RU58841的合成工艺研究
王晓霞1,2，曹碧霞1,2，杨欣梓1,2，李泽坤3，刘荣*1,2
(1. 甘肃省化工研究院有限责任公司，甘肃 兰州 730020；2. 甘肃省精细化工重点实验室，甘肃 兰州 730020；3. 西北民族大学 化工学院，甘肃 兰州 730030)
摘要：乙内酰脲是一种具有广泛的生物和药理活性，且具有4个功能点的五元杂环化合物。这种小而刚性的骨架可以有效地作用于各种药理靶点，几种临床上重要的药物如苯妥英（抗癫痫药）、阿齐利特（抗心律失常药）和尼鲁米特（抗雄激素药）等都是基于这种特征性的主要骨架。RU58841（IUPAC 名称：4-[3-（4-羟基丁基）-4,4-二甲基-2,5-二氧咪唑啉-1-基]-2-（三氟甲基）苯甲腈）是一种具有抗秃发活性的乙内酰脲衍生物，证据表明RU58841几乎没有毒性，有望成为一种新的外用非甾体抗雄激素。研究发现以4-氨基-2-(三氟甲基)苄腈为原料，通过三光气制备异氰酸酯、[3+2]环加成、N -烷基化和脱保护共4步反应制备RU58841，总产率为40%。与传统方法相比，该方法可以更方便、更安全地获得RU58841。
关键词：三光气；乙内酰脲；RU58841；[3+2]环加成；抗秃发剂
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2022）--
A New Method for Synthetic Methods of Hydantoin Derivative RU58841 WANG Xiao-xia1,2, CAO Bi-xia1,2, YANG Xin-zi1,2, LI Ze-kun3, LIU Rong *1,2 (1. Gansu Chemical Industry Research Institute Co. Ltd., Lanzhou 730020, China; 2. Key Laboratory of Fine Chemicals, Gansu Province. Lanzhou 730020, China; 3. Department of Chemistry, Norhwest Minzu University, Lanzhou 730030, China), Huaxue Shiji, 2022, 44(9), ～
Abstract：Hydantoinis, a five-membered heterocyclic compound with four functional points, show various amazing biological and pharmacological activity. This small and rigid backbone could effectively act on various pharmacological targets. Several clinically important medicines such as phenytoin (antiepileptic), azimilide (antiarrhythmic) and nilutamide (antiandrogen) are based upon this characteristic staple scaffold. RU58841(IUPAC name: 4‐[3‐(4‐hydroxybutyl)‐4,4‐dimethyl‐2,5‐dioxoimidazolidin‐1‐yl]‐2‐(trifluoromethyl)benz onitrile) was found active against baldness with little evidence of toxicity, and it has promise as a new topically active non-steroidal antiandrogen. In this paper, we report a new alternative synthesis of RU58841. RU58841 was synthesized using 4-amino-2-(trifluoromethyl) benzonitrile as raw material in 4 steps including the preparation of isocyanate, [3+2] cycloaddition, N-alkylation and deprotection with over-all yield of 40%. Compare to traditional method, the method can be more convenient and safer to get RU58841.
Key words：triphosgene; hydantoin; RU58841; [3+2] cycloaddition; against baldness
引用本文：王晓霞，曹碧霞，杨欣梓，等. 乙内酰脲衍生物RU58841的合成工艺研究[J]. 化学试剂，2022,44（9）:1398-1402.
