电化学手性识别材料的研究与应用

杨洋，朱志伟^*

（北京大学 化学与分子工程学院，北京  100871）

摘要：手性是指物质分子互成镜像但无法重合的性质，手性对映体在生物体内因不同的手性识别而呈现截然不同的作用，所以手性识别在生命科学、医药、食品及材料等领域均具有十分重要的科学意义。手性电化学传感器由于具有制备简单、检测快速和响应灵敏等优点而引起广泛的关注。手性识别材料是构建手性电化学传感器的基础，因此有关手性识别材料的研究在手性电化学检测中尤为重要。综述了近五年的手性电化学传感器研究进展，详细介绍了多种手性识别材料的具体应用，并对该领域的发展前景进行了展望，旨在为今后手性电化学传感器的设计提供参考。

关键词：手性；手性识别；手性识别材料；电化学传感；手性电化学传感器；进展

中图分类号：O657.1     文献标识码：A   文章编号：0258-3283（2021）

Research and Application of Electrochemical Chiral Recognition Materials

YANG Yang, ZHU Zhi-wei*(College of Chemistry and Molecular Engineering, Peking University, Beijing100871)

Abstract: Chirality refers to the properties of molecules that mirror each other but cannot coincide with each other. Chiral enantiomers have completely different functions in organisms due to different chiral recognition. Chiral recognition is of great scientific significance in the fields of life science, pharmacy, food and materials. Electrochemical chiral sensors have attracted wide attention due to their advantages of simple preparation, rapid detection and sensitive response. Chiral recognition materials are the basis of the construction of chiral electrochemical sensors, andthe study regardingthese materials is particularly important in the electrochemical chiral sensing. In this paper, the research progress of electrochemical chiral sensors in the past five years is reviewed, the application of various chiral recognition materials is introduced in detail, and the development prospect of this field is prospected,aiming to provide reference for the design of electrochemical chiral sensorsinthefuture.

Key words: Chirality; Chiral recognition; Chiral recognition material; Electrochemical sensing; Electrochemical chiral sensor; Progress

均苯三甲酸银[{Ag(H₂btc)}{Ag₂(Hbtc)}]_n配位聚合物的光催化性能和抗菌性能研究

解蓉蓉，杨廷海，冯婕，张曼莹^*

(江苏理工学院 化学与环境工程学院，江苏 常州  213001）

摘要：采用1,3,5-苯三甲酸（H₃btc）与硝酸银（AgNO₃）在MeOH/H₂O混合溶液中通过自组装反应构建出[{Ag(H₂btc)}{Ag₂(Hbtc)}]_n配合物。利用扫描电镜（SEM）、X-射线粉末衍射仪（XRD）、傅里叶变换红外光谱（FT-IR）对材料的形貌和组成进行表征。以亚甲基蓝（MB）和罗丹明B（RhB）为脱色降解模型，测定样品的可见光下光催化降解性能。通过抑菌环、生长曲线和最小抑菌浓度检测其抗菌性能。结果表明：所得的化合物材料纯度较高，具有良好的可见光下光催化性能和抗菌性能。

关键词：金属有机骨架；银；光催化；染料降解；抗菌

中图分类号：X522     文献标识码：A    文章编号：0258-3283（2021）

Photocatalytic and Antibacterial Properties of Silver Complex with 1,3,5-Benzenetricarboxylic Acid [{Ag(H₂btc)}{Ag₂(Hbtc)}]_n

XIE Rong-rong，YANG Ting-hai，FENG Jie，ZHANG Man-ying^*(Department of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001, China)

Abstract: Self-assembly reaction of 1,3,5-benzenetricarboxylic acid (H₃btc) with AgNO₃ in mixed MeOH/H₂O solution at room temperature gave rise to a sliver(Ⅰ) complex [{Ag(H₂btc)}{Ag₂(Hbtc)}]_n. The morphology and composition were characterized by X-ray powder diffractometer (XRD), Scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). Methylene blue (MB) and rhodamine B (RhB) were used as the decolorization and degradation models to determine the photocatalytic performance of samples with different silver contents under visible light. The antibacterial performance was tested by the bacteriostatic ring, growth curve and minimum bacteriostatic concentration. The results show that the obtained compound material has high purity, od photocatalytic performance under visible light and antibacterial performance.

Key words：MOF；Silver；Photocatalytic；Dye degradation；Antibacterial

Btk/JAK3双靶点共价抑制剂的设计、合成及其活性研究

曹思思¹，张洁¹，曾宪霞¹，黄怀怔¹，岳晓阳²，何林洪^*1

（1. 广西医科大学 药学院；2. 广西医科大学 基础医学院，广西 南宁 530021）

摘要：布鲁顿式酪氨酸激酶（Btk）和两面神激酶3（JAK3）均是自身免疫性疾病和血液系统恶性肿瘤的潜力靶标。以4-氯吡咯并嘧啶为原料，经7步反应合成了一系列7H-吡咯并[2,3-d]嘧啶-4-胺衍生物，其结构经¹HNMR、¹³CNMR和MS（ESI）分析证实。体外依次考察了所得化合物分别对Btk和JAK3激酶的活性、以及对部分B淋巴细胞瘤细胞系的抗增殖活性。结果表明，四氢吡咯烷基取代的衍生物NB1～4对Btk（IC₅₀< 3 nmol/L）和JAK3（IC₅₀< 165 nmol/L）均能有效抑制，其余化合物只对Btk显示抑制效果；而且，NB2和NB4对所测试的多种B细胞淋巴瘤细胞系的抗增殖活性均优于阳性对照泛激酶抑制剂依鲁替尼及Btk单靶点抑制剂，其中，对Jeko-1细胞的抑制能力最佳（IC₅₀< 3 μmol/L），其次是OCI-LYI（IC₅₀< 4 μmol/L）、 SUDHL-6 （IC₅₀< 6 μmol/L）和 HBL-1*（IC₅₀< 6.5 μmol/L），最差为SUDHL-4细胞（IC₅₀< 11 μmol/L）。这些发现可为开发B细胞淋巴瘤的多靶点药物提供新的思路。

关键词：Btk, JAK3,双靶点, 共价抑制剂, B细胞淋巴瘤

中国分类号：0626.13   文献标识码：A    文章编号：0258-3283(2021)—

Design, Synthesis and Bioactivity of Btk/JAK3 Dual Target Covalent Inhibitors

Cao Si-si¹, Zhang Jie¹, Zeng Xian-xia¹, Huang Huai-zheng¹, Yue Xiao-yang², He Lin-hong¹ (¹Pharmaceutical College, ²School of Basic Medical Sciences, Guangxi MedicalUniversity, Nanning, Guangxi, 530021, China) , Huaxue Shiji, 2021, 43(1), ～

Abstract:Bruton's tyrosine kinase (Btk) and Janus kinase 3 (JAK3) are very promising targets for hematological malignancies and autoimmune diseases. A seriesof 4-amino-7H-pyrrolo[2,3-d]pyrimidine derivatives were synthesized via seven steps, by using 4-chloro-7H-pyrrolo[2,3-d]pyrimidine as raw material, and all the targetcompounds were confirmed by¹H-NMR, ¹³C-NMR and MS(ESI). The bioactivity tests against Btk and JAK3 were carried out, as well as the anti-proliferative ability against selected B-cell lymphoma. Among them, derivatives substituted with tetrahydropyrrolidinyl NB1-4 significantly inhibited Btk (IC₅₀< 3 nmol/L)and JAK3 (IC₅₀< 165 nmol/L); others can only inactive Btk. Moreover, both compounds NB2 and NB4 showed strong activities to block the proliferation of B-cell lymphoma sells compared with the positive control pan-inhibitor ibrutinib and other Btk inhibitors. The inhibitory potency against Jeko-1 was the best, followed by OCI-LYI(IC₅₀< 4 μmol/L), SUDHL-6 (IC₅₀< 6 μmol/L)and HBL-1*( IC₅₀< 6.5 μmol/L)，while SUDHL-4 being the worst. These findings could provide a new insight for the developmentof novel anti-B-cell lymphoma drugs with multi-target actions.

Key words: Btk, JAK3,double target,covalent inhibitor,B-cell lymphoma

羟基磷灰石作为催化材料的研究进展

任大军^*，尚珊珊

（武汉科技大学 资源与环境工程学院，湖北 武汉  430081）

摘要：羟基磷灰石（HAP）由于具有无毒性、生物相容性、热稳定性、吸附性、离子交换性、结构稳定性等性能，而被应用到催化剂的制备中。作为一种新型催化材料，HAP的特殊晶体结构对一些反应表现出催化活性，并且，经过改性、负载等方法处理过后的HAP催化剂显示出独特的催化优势。基于近年来HAP在催化邻域的发展，综述了HAP作为催化材料的在降解污染物、制氢、药物合成、还原氮氧化物等反应中的不同应用，并对以后的研究方向进行了展望。

关键词：羟基磷灰石；结构活性；催化；应用

中图分类号：O643.3     文献标识码：A      文章编号：0258-3283（2021）

Progress of Hydroxyapatite as Catalytic Material

REN Da-jun^*, SHANG Shan-shan (College of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China), Huaxue Shiji, 2021, 43(1),  ～

Abstract: Hydroxyapatite (HAP) has been used in the preparation of catalysts due to its excellent properties such as non-toxicity, biocompatibility, adsorption, and ion exchange. As a new type of catalytic material, the special crystal structure of HAP shows catalytic activity for some reactions, and the HAP catalyst treated by modification, loading and other methods shows unique catalytic advantages. Based on the development of HAP in the catalytic neighborhood in recent years, the different applications of HAP as a catalytic material in the degradation of pollutants, hydrogen production, drug synthesis, and reduction of nitrogen oxides are reviewed, and the future research directions are prospected.

Key words: hydroxyapatite; structure-activity; catalysis; application

胆汁淤积性肝病治疗药物的临床研究进展

刘洪涛^*a，杨玉鹏^b，任炳楠^a

（河北省人民医院 a. 药学部，b. 口腔科，河北石家庄050051）

摘要：胆汁淤积性肝病是指由各种原因导致胆汁形成、分泌、排泄异常，从而引起肝脏发生病变。目前，治疗胆汁淤积性肝病的药物主要为熊去氧胆酸（UDCA），但近一半的患者对UDCA应答不充分或不耐受。这部分患者仅有奥贝胆酸（OCA）可用。随着近几年胆汁淤积性肝病的发病率明显上升，急需新型有效的治疗药物。临床研究表明，FXR激动剂、PPARα/γ激动剂和ASBT抑制剂能够有效改善胆汁淤积，有望成为新型胆汁淤积性肝病的临床治疗药物。针对以上靶点，对近几年较有前景的胆汁淤积性肝病治疗药物临床研究进展进行了综述，为此类药物的研究提供参考。

关键词：胆汁淤积性肝病；胆汁酸；原发性胆汁性胆管炎；原发性硬化性胆管炎

中图分类号：O626文献标识码：A      文章编号：0258-3283（2021）

Progress inClinical Research on Drug Therapy for CholestaticLiver Disease

LIU Hong-tao^*a, YANG Yu-peng^b, REN Bing-nan^a (a. Department of Pharmacy, b. Department of Stomatology, Hebei General Hospital, Shijiazhuang 050051, China), HuaxueShiji, 2021, 43(1),    ～

Abstract: Cholestatic liver disease refers to the abnormal formation, secretion and excretion of bile caused by various reasons, resulting in liver lesions. Currently, ursodeoxycholic acid (UDCA) is the main drug used to treat cholestatic liver disease, but nearly half of patients have inadequate or intolerant response to UDCA.Only aubercholic acid (OCA) was available in these patients.With the increasing incidence of cholestatic liver disease in recent years, there is an urgent need for the development of new effective therapeutic drugs.Clinical studies have shown that FXR anists, PPAR α/γ anists and ASBT inhibitors can effectively improve cholestasis and are expected to be used as therapeutic agents for the new type of cholestatic liver disease.Aiming at the above targets, this workreviews the promising clinical research progress in the treatment of cholestatic liver disease in recent years, so as to provide reference for the research of this kind of drugs.

Key wordscholestatic liver disease; bile acid; primary biliary cholangitis; primary scle-rosing cholangitis

Suzuki偶联反应合成沙坦联苯研究进展

刘鸿坤，刘雷芳，侯梦圆，程自强，李龙珠，张杨，李文波^*

（德州学院 化学化工学院，山东 德州  253023）

摘要：沙坦联苯，即2-氰基-4’-甲基联苯，是抗高血压药物沙坦类药物的关键中间体。通过对沙坦联苯的结构进行衍生和修饰，可得到大多数沙坦类药物。因此，沙坦联苯的合成方法一直是有机合成化学家关注的热点研究领域。Suzuki偶联反应是合成沙坦联苯最重要的方法之一。近二十年来，文献中出现了大量利用Suzuki偶联反应合成沙坦联苯的催化体系。为了让大家更好的掌握目前利用Suzuki偶联反应合成沙坦联苯的现状，根据原料的不同，从不同卤代芳烃角度对沙坦联苯的合成方法进行了综述，以期对同行工作者有所启发和帮助。

关键词：沙坦联苯；合成方法；研究进展；Suzuki偶联反应        

中图分类号：O625.13      文献标识码：A      文章编号：0258-3283（2021）--

Progress on Synthesis of Sartanbiphenyl via Suzuki Coupling Reactions

 LIU Hong-Kun, LIU Lei-Fang, HOU Meng-Yuan, ChENG Zi-Qiang, LI Long-Zhu, ZHANG Yang, LI Wen-Bo* (College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China), Huaxue Shiji, 2021, 43(1), ～

Abstract：Sartanbiphenyl, namely 2-cyano-4'-methylbiphenyl, is the key intermediate for antihypertensive sartan drugs. Most sartan drugs could be prepared by the derivations and modifications of Sartanbiphenyl. Therefore, the synthesis of sartanbiphenyl is always being a hot topic for the organic synthetic chemists. Suzuki coupling reaction is one of the most important synthetic methods for sartanbiphenyl and lots of catalytic systems have been reported in literatures in recent twenty years. This work should be helpful for the researchers of sartanbiphenyl, reviewed the synthetic methods of sartanbiphenyl via Suzuki coupling reaction based onthe raw materials used.

Key words：Sartanbiphenyl; synthetic method; research progress; Suzuki coupling reaction

雪松醇的合成应用及其药理作用研究进展

汤陆扬¹，卢小鸾¹，杨敏^*1，付阳洋¹，孙晓霞¹，彭黔荣^*2，杨培昕¹

（1.贵州大学药学院，贵州 贵阳 550025； 2.贵州中烟工业有限责任公司技术中心, 贵州 贵阳 550000）

摘要：雪松醇（Cedrol, CE），一种用途极为广泛的天然倍半萜醇，广泛存在于柏科、杉科及松科等多种植物的挥发油中。研究报道CE存在多种药理作用，包括抗炎镇痛、对心脑血管系统作用、抗肿瘤、促进头发生长、抗菌、抗疟原虫活性等。为拓宽其应用，加速其新药研发进程，有必要对其研究进行总结。通过查阅相关文献，归纳总结了CE的提取与检测以及其在合成中的应用，探讨了近年来CE的药理作用及其可能的作用机制，并分析了其未来发展方向，为其应用以及新药研发提供参考。

关键词：雪松醇；提取与检测；合成；药理作用

中图分类号：R285     文献标识码：A    文章编号：0258-3283（2021）--

Progress on Synthesis Application and Pharmacological Effectsof Cedrol

Tang Lu-Yang^1, Lu Xiao-Luan^1, Yang Min^*1, Fu Yang-Yang^1, Sun Xiao-Xia^1, Peng Qian-Rong^*2, Yang Pei-Xin¹ (1. School of Pharmacy, Guizhou University, Guizhou Guiyang 550000; 2.Technical Center of China Tobacco Guizhou Industry Co. Ltd, Guizhou Guiyang 550000), Huaxue Shiji, 2021, 43(1), ～

Abstract: Cedrol (Cedrol, CE), a natural sesquiterpene alcohol with a very wide range of uses, is widely present in the volatile oils of various plants such as Cupressaceae, Taxaneae and Pinaceae. CE has a variety of pharmacological effects, including anti-inflammatory and analgesic effects, effects on the cardiovascular and cerebrovascular systems, anti-tumor, hair growth promotion, antibacterial, and anti-plasmodium activities. In order to broaden its application and accelerate its new drug development process, it is necessary to summarize it. This work summarizes the extraction and detection of CE and its application in synthesis by consulting related literature, discusses the pharmacological effects and possible mechanisms of CE in recent years, and analyzes its future development direction, its application and new drugs R & D provides reference.

Keywords: cedrol; extraction and detection; synthesis; pharmacological effects;

药用辅料的管理及其研究新进展

潘波¹，顾小焱²，刘征宙^*2

（1.国药控股股份有限公司, 上海  200002；2. 国药集团化学试剂有限公司，上海  200002）

摘要：药用辅料的管理及其研究对我国医药产业发展具有重要作用。新版《中国药典》构建了药用辅料功能性相关指标的标准体系，对药用辅料产业链上企业的研发、产业化与流通以及应用具有深远意义。尤其在试剂与医药流通领域，药用辅料管理处于生产与应用之间，掌握药典规范药用辅料标准以及药用辅料标准体系建设至关重要。通过梳理药用辅料研究进展，了解药用辅料科研方法，进而更深入研究药用辅料相关问题，同时也为药用辅料行业高质量发展提供参考和借鉴。

关键词：药用辅料；药物制剂；试剂；标准；医药流通；检测；应用进展

中图分类号: R914. 4     文献标识码: A    文章编号:

Management and Research Progress of Pharmaceutical Excipients

PAN Bo¹, GU Xiao-yan², LIU Zhen-zhou^*2（1.Sinopharm Group Co., Ltd., Shanghai 200002, China; 2.Sinopharm Chemical Reagents Co., Ltd., Shanghai 200002, China）, HuaxueShiji, 2020, 42(1)

Abstract: The management and research progress of pharmaceutical excipients play an important role in the development of China's pharmaceutical industry. The new edition of Chinese Pharmacopoeia establishes the standard system of functional indicators of pharmaceutical excipients, which is of great importance to the research and development, industrialization, circulation and application of enterprises in the pharmaceutical excipients industry chain, Especially in the field of reagent and pharmaceutical circulation, it is very important to manage the pharmaceutical excipients between production and application, and master the standard system construction of pharmaceutical excipients in Pharmacopoeia. To sort out the research progress of pharmaceutical excipients and understand the scientific research methods of pharmaceutical excipients is to further study the related problems of pharmaceutical excipients and provide reference for the high-quality development of pharmaceutical excipients industry.

Key words: pharmaceutical excipients; pharmaceutical preparations; reagents; standards; pharmaceutical circulation; detection; application progress

UPLC-HRMS法同时测定α-核糖甲磺酸酯中D-甘露醇和双丙酮-甘露醇含量

李林喆^1a，毛联岗²，姚彤²，刘梦婷²，顾娜^1b，季春伟^1b，张珍明^{1b, 3}，李树安^{*1b, 3}

（1. 江苏海洋大学 a. 海洋生命与水产学院；b. 化学工程学院，江苏 连云港  222005；

2. 连云港杰瑞药业有限公司，江苏 连云港  222006；

3. 江苏省海洋资源开发研究院，江苏 连云港  222005）

摘要：建立了同时测定盐酸吉西他滨合成原料α-核糖甲磺酸酯中杂质D-甘露醇和双丙酮-甘露醇含量的超高效液相色谱-高分辨质谱法。采用菲罗门Titank C₁₈色谱柱，以70%乙腈水溶液（甲酸调至pH3.0）为流动相，流速0.9 mL/min，柱温45 ℃。质谱为电喷雾（ESI）离子源，正离子模式扫描，外标法定量。本法D-甘露醇和双丙酮-甘露醇分别在1.00～12.53、0.99～12.42 μg/mL浓度范围内线性关系良好，相关系数r分别为0.9998和0.9979，平均加标回收率分别为100.9%和99.5%。方法快速便捷、专属性强、灵敏度高、重现性好、结果准确可靠。

关键词：超高效液相色谱-高分辨质谱；盐酸吉西他滨；α-核糖甲磺酸酯；D-甘露醇；双丙酮-甘露醇；含量测定

中图分类号：R917      文献识别码：A      文章编号：0258-3283（2021）--

Simultaneous Determination of D-Mannitol and Diacetone Mannitol in α-Ribose Methyl Methanesulfonate by UPLC-HRMS

LI Lin-zhe^1a, MAO Lian-gang², YAO Tong², LIU Meng-ting², GU Na^1b, JI Chun-wei^1b, ZHANG Zhen-ming^1b,3, LI Shu-an^*1b,3 (1.a. School of Marine Life and Fisheries; b. School of Chemical Engineering, Jiangsu Ocean University, Lianyungang 222005, China; 2. JARI Pharmaceutical Co., Ltd., Jiangsu Lianyungang, 222006; 2. Jiangsu Institute of Marine Resources, Jiangsu Lianyungang, 222005)

, Huaxue Shiji, 2021, 43(1), ～

Abstract: A method was established for the simultaneous determination of D-mannitol and diacetone mannitol in α-Ribose methyl methanesulfonate, a raw material for synthesis of Gemcitabine hydrochloride, by ultra performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). The analysis was performed on a Titank C₁₈ column by using 70% acetonitrile solution (pH 3.5) as mobile phase at a flow rate of 0. 9 mL/min and a column temperature of 45 ℃. The mass spectrometry used electrospray ionization and positive ion scanning mode. The contents were calculated by external standard method. The calibration curves for D-mannitol and diacetone mannitol showed od linearity in the ranges of 1.00~12.53 μg/mL and 0.99 ~ 12.42 μg/mL, with their correlation coefficients of 0.9998 and 0.9979, respectively. The average spiked recoveries for D-mannitol and diacetone mannitol were 100.9% and 99.5%, respectively. The method is efficient, convenient, sensitive, reproducible, accurate and reliable.

Key words: UPLC-HRMS; Gemcitabine hydrochloride; α-Ribose methyl methanesulfonate; D-mannitol; diacetone-mannitol; content determination

柠檬桉叶的HS-SDME-GC/MS谱图及其主成分分析

王聪

（杭州职业技术学院 临江学院，浙江 杭州 310018）

摘要：采用顶空单液滴微萃取-气相色谱/质谱法（HS-SDME-GC/MS）测定了13个不同产地的柠檬桉叶并结合主成分分析法建立判别模型，采正交法优化其实验条件。结果表明，单液滴微萃取优化条件为：10 mL顶空瓶中1.0 g样品、60 ℃顶空40 min，苯甲酸乙酯吸附进而吸收柠檬桉叶中的化学物质，比对NIST 14谱库并结合相关文献鉴定柠檬桉叶种的30种化学成分，化学成分按照烯类、醇类、酯类和醛类进行分类，并建立主成分分析判别模型。方法简单、快速、准确，对天然产物进行有效的产地溯源，实用性良好。

关键词：顶空单液滴微萃取-气相色谱/质谱法；正交试验；主成分分析；柠檬桉叶

中图分类号：O657.7      文献标识码：A      文章编号：0258-3283（2021）--

HS-SDME-GC/MS Chromatogram and Principal Component Analysis for Eucalyptus CitriodoraHook.f. Leaves

 WANG Cong (Hangzhou Vocational & Technical College, Hangzhou 310018, China) , Huaxue Shiji, 2021, 43(1), ～

Abstract： The samples of eucalyptus citriodora Hook.f. leaves from thirteen different regions were analyzed by headspace -single drop microextraction - gas chromatography / mass spectrometry (HS-SDME-GC/MS). Then principal component analysis (PCA) discriminant model was established. At the same time, the experimental conditions were optimized via orthonal method. An amount of 1.0 g raw powder in 10 mL headspace vial was heated up to 60 degrees for 40 min, meanwhile the compounds of Eucalyptus citriodora Hook.f. leaves were volatilized and then adsorbed by the single drop of ethyl benzoate. The sample drop was directly introduced into a gas chromatograph equipped with a fused-silica capillary column(30 m× 0.25 mm×0.25μm)． Mass spectroscopy was applied to characterize 30 components in samples by referring to the NIST 14 mass spectrometry database and related literatures. In summary, HS-SDME-GC/MS with PCA can be used to identify regions and has great practicability. Thus，the results proved HS-SDME-GC/MS is a simple，rapid and accurate method.

Key words: headspace -single drop microextraction - gas chromatography / mass spectrometry (HS-SDME-GC/MS)； orthonal method； principal component analysis (PCA)； eucalyptus citriodora Hook.f. leaves

库仑滴定法测定生物乙醇制备原料的还原糖含量

王林郁^*1，黄学梅²

（1. 长治职业技术学院 采选煤工程系，山西 长治  046011；2. 长治学院 化学系，山西 长治  046011）

摘要：利用库仑滴定法测定生物乙醇原料蔗糖的还原糖含量。样品经5 mL 10%盐酸于65 ~ 70 ℃水解15 min 后，以铂电极为电解电极和指示电极，1.0 mol/L硫酸亚铁为电解质溶液 (pH 2.0)，恒电流电解生成Fe³⁺，与预处理样品后生成的氧化亚铜定量发生氧化还原反应，记录电解至滴定终点时间，通过法拉第电解定律，计算样品中还原糖含量。利用该方法分别测定不同蔗糖样品还原糖含量，结果与高锰酸钾滴定法无显著性差异，相对标准偏差均低于2.0%，因此适于生物乙醇生产前原料的质量控制。

关键词：库仑滴定；生物乙醇；蔗糖；还原糖；原料

中图分类号：O657.12     文献标识码：A    文章编号：0258-3283（2021）

Determination of Reducing Sugar Content in Raw Material for Bioethanol Production by Coulometric Titration

WANG Lin-yu^*1, HUANG Xue-mei² (1. Department of Coal Mining Engineering, Changzhi Zhiye Jishu Xueyuan, Changzhi 046011, China; 2. Department of Chemistry, Changzhi College, Changzhi 046011, China), Huaxue Shiji, 2021, 43(1),    ～

Abstract: A novel method that coulometric titration to rapid determine content of reducing sugar content in raw material for bioethanol production is described. The sample is hydrolyzed by 5 mL hydrochloric acid that concentration was 10% in 65 ~ 70 ℃ sustaining fifteen minutes. Two couple of platinum electrode is served as electrolysis electrode pairs and indicating electrode pairs respectively, 1.0 mol/L ferrous sulfate solution (pH 2.0) act as the electrolyte solution. the iron ion is generated by the ferrous sulfate solution electrolysis through constant current quantitatively react with cuprous oxide generated after sample pretreatment, which is oxidation-reduction reaction. The result is obtained by Faraday’s law through electrolysis time that titrated to titration end-point. In optimum analytical conditions, the reducing sugar contents of different samples were measured by coulometric titration and potassium permanganate method. The two methods results have no significant difference, and the relative standard deviations of coulometric titration were lower than 2.0%. Therefore, the proposed method will be very useful for the quality control of raw material before bioethanol production.

Key words: coulometric titration; bioethanol; sucrose; reducing sugar; raw material

采用ICP-AES法测定低钢、不锈钢和铁基高温合金中铈含量

张亮亮^*，吴锐红，张方

(中航金属材料理化检测科技有限公司，陕西 西安  710018)

摘要：为了从铈的谱线列表中选取合适分析线，以实现铁基样品中铈的准确测定。实验采用电感耦合等离子体原子发射光谱（ICP-AES）法和干扰系数（IEC）模型相结合，建立了低钢、不锈钢和铁基高温合金中铈含量的测试方法。在已优化的仪器参数条件下，通过对铈系列标准溶液和不同牌号的铁基样品进行分析，可选取380.152、401.239、404.076、413.765 nm作为测定铁基样品中铈的分析线，并进一步研究了这4条谱线下酸的影响与共存元素的干扰行为。结果表明：在测定低钢时优选401.239 nm为分析线，不锈钢优选401.239 nm（Cr干扰）和413.765 nm（W干扰），铁基高温合金选取404.076 nm和413.765 nm（W干扰），并对存在元素干扰的分析线实施干扰校正后，曲线的线性关系得到极大改善，且铁基样品的测定结果满足准确度要求。

关键词：电感耦合等离子体原子发射光谱（ICP-AES）；干扰系数法（IEC）；铁基样品；铈；光谱干扰

中图分类号：O657.31    文献标识码：A   文章编号：0258-3283（2021）

Determination of Cerium Content in Low Steel, Stainless Steel and Iron-base Superalloy by ICP-AES Method

ZHANG Liang-Liang^*, WU Rui-Hong, ZHANG Fang (AVIC Metal Test Technology Company Limited, Xi'an 710018, China )

Abstract: In order to select the appropriate analysis lines from the spectrum list of cerium, the accurate determination of cerium can be realized in the iron-base samples. The determination method of cerium in low steel, stainless steel and iron-base superalloy by inductively coupled plasma atomic emission spectrometry (ICP-AES) method-interference coefficient method (IEC) model was established. Under the condition of optimized instrument parameters, by analyzing cerium series standard solution and different grades of iron-base samples, 380.152 nm, 401.239 nm, 404.076 nm and 413.765 nm were chosen as the analysis lines for the determination of cerium in iron-base samples, moreover, the effect of acids and the interfering behavior of co-existing elements were further investigated at the four spectral lines. The results showed that it is preferable to choose 401.239 nm as the analysis line in the determination of low steel, 401.239 nm (chromium interference) 413.765 nm (tungsten interference) as the analysis line in stainless steel, and 404.076 nm and 413.765 nm (tungsten interference) as the analysis line in iron-base superalloy. The linear relationship of the calibration curve was greatly improved after the interference correction of the analysis lines with element interference, and the determination results of iron-base samples met the requirements of accuracy.

Key words: inductively coupled plasma atomic emission spectrometry (ICP-AES); interference coefficient method (IEC); iron-base samples; cerium; spectral interference

商品化酶抑制-比色法农残速测试剂盒对农药的敏感性测定

罗俊霞¹，赵建波^*2，唐国林³，辛焕发³，宋晓爽¹，张刚⁴，梁爽⁴

（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  450006；3. 深圳市安鑫宝科技发展有限公司，广东 深圳  518000；4. 河南恒晟检测技术有限公司，河南 郑州  450011）

摘要：探讨商品化的酶抑制-比色法农残速测试剂盒对50种农药的敏感性。使用商品化的酶抑制-比色法试剂盒对嘧啶磷等40种有机磷和10种氨基甲酸酯类农药残留进行5个浓度水平的测定；对有3个浓度水平的抑制率大于0的农药，用抑制率和农药浓度的常用对数进行线性拟合，得出相关系数和抑制率方程，并据此计算IC₁₀和IC₅₀，通过IC₁₀比较试剂盒对各种农药的灵敏度。所选用的试剂盒对每种农药的敏感性不相同；就IC₁₀看，在检测中取用3和2.5 mL的样品溶液也有差别，个别农药的差别在1或者2个数量级。建议使用者在购置试剂盒时根据需要对试剂盒进行测试。

关键词：酶抑制-比色法；农药残留；重现性；灵敏度；复检

中图分类号：O656       文献标识码：A      文章编号：0258-3283（2021）

Sensitivity Determination of Pesticide by Commercial Enzyme Inhibition Colorimetric Method

LUO Jun-xia¹, ZHAO Jian-bo^*2, TANG Guo-lin³, XIN Huan-fa³, SONG Xiao-shuang¹, ZHANG Gang⁴, LIANG Shuang⁴ (1. Zhengzhou Agricultural Product Quality Testing and Distribution Center, Zhengzhou 450006, China; 2. Zhengzhou Agricultural Technology Extension Centre, Henan 450002, China; 3. Shenzhen Anxinbao Technology Development Co., Ltd, Shenzhen 518109, China; 4. Henan Hengsheng Testing Technology Co., Ltd., Zhengzhou 451100, China), Huaxue Shiji, 2021, 43(1),   ～

Abstract: Objective: To investigate the sensitivity of commercial enzyme inhibitor-colorimetry agrochemical residue test kit to 50 kinds of pesticides. Methods: It was tested with commercial enzyme inhibition colorimetric kit at five concentration levels in 40 kinds of organophosphorus and 10 kinds of carbamate pesticide residues, such as pyrimidine phosphate；For pesticides with inhibition rates greater than 0 at three concentration levels， the common logarithm of inhibition rate and pesticide concentration was used for linear fitting to obtain the correlation coefficient and inhibition rate equation, and then IC₁₀ and IC₅₀ were calculated accordingly，and the sensitivity of the kit to various pesticides was compared by IC₁₀. Results: The selected kits have different sensitivities to each pesticide; For IC₁₀, there is also a difference between 3mL and 2.5ml sample solutions, and the difference of individual pesticides is one or two orders of magnitude. It is recommended that users test the kit as needed when purchasing the kit.

Key words: enzyme inhibition colorimetry; pesticide residue; reproducibility; sensitivity; test

组合称重法与分压法的C₅F₁₀O-PFK/Air混气制备技术研究

朱会¹，齐汝宾^1,2，曾晓哲¹，赫树开¹，吴倩倩^*1，侯新梅¹

(1.河南省日立信股份有限公司，河南 郑州  450001；2.郑州轻工业大学 电气工程学院，河南 郑州  450002)

摘要：制备高精度的C5-PFK/Air混合气体有利于实现对C5-PFK气体-电气性能的科学论证。采用称重法与分压法实现了对不同混合比的C5-PFK/Air混合气体的制备，搭建C5-PFK/Air混气制备实验系统，建立了气相色谱-氢火焰离子化检测器（GC-FID）对制备的C5-PFK/Air混气中C5-PFK定性定量分析的仪器方法，可对实验结果进行溯源校准。研究结果表明：制备13% C5-PFK/Air混合气体的RSD为0.89%，最大示值误差为0.77%；压力为0.5 MPa时，12%～15%浓度范围内C5-PFK/Air混气中C5-PFK峰面积线性拟合系数R²为0.995，一致性良好，可完全汽化；6个月的稳定性考察，气体特性值保持不变，稳定性良好。

关键词：称重法；分压法；GC-FID；重复性；均匀性；稳定性；C5-PFK/Air       

中图分类号： X830.5      文献标识码：A      文章编号： 0258-3283（2021）--

Preparation Technology of C5F10O-PFK/Air Mixture by Combining Weighing Method and Partial Pressure Method

ZHU Hui¹, QI Ru-bin^1,2, ZENG Xiao-zhe¹, HE Shu-kai¹, WU Qian-qian^*1, HOU Xin-mei¹ (1. Henan Relations Co.，Ltd.，Zhengzhou 450001, China; 2. College of Electric Information Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China), Huaxue Shiji, 2021, 43(1), ～

Abstract：The preparation of high precision C5-PFK/Air mixture is beneficial to the scientific demonstration of the electrical properties of C5-PFK gas.Weighing method and partial pressure method were used to realize the preparation of C5-PFK /Air mixed gas with different mixing ratios. An experimental system was established for the preparation of C5-PFK/Air mixed gas. A gas chromatography-hydrogen flame ionization detector (GC-FID) was established for the qualitative and quantitative analysis of C5-PFK in the prepared C5-PFK/Air mixture, which can be used for the source calibration of the experimental results. The RSD for preparing 13% C5-PFK/Air mixture was 0.89%, and the maximum indicating error was 0.77%. When the pressure was 0.5MPa, the linear fitting coefficient R² of the peak area of C5-PFK in the C5-PFK /Air mixture was 0.995 with od consistency and complete vaporization. The gas characteristic value remained unchanged and stable during the 6 months stability investigation.

Key words： weighing method; partial pressure method; GC-FID; repeatability; uniformity; stability; C5-PFK/Air 

TD-GC/MS法研究气、液相标准物质对环境空气中苯系物含量测定的差异影响

魏王慧，董翊，于瑞祥，姜阳，任逸尘，高艳秋，陈鹰^*1

（上海市计量测试技术研究院，上海 201203）

摘要：使用热脱附-气相色谱/质谱法，探究了气、液相标准物质对气体样品中苯系物测定的差异影响。分别绘制了7种苯系物气、液相标准物质的校准曲线，发现液相标物中各苯系物的响应明显高于气相标物。通过一系列猜想的提出及穿透实验、二次解析、甲醇试验等的试验验证，认为甲醇大量电离形成的高能量氛围，提高了苯系物的电离能力，使得液相标物响应增大。因此气相标准物质比液相标准物质更适合环境空气等气体样品中苯系物的定量检测。最后还通过精密度实验进一步验证了气相标准物质方法的可靠性，并给出了最优样品采集速率为100 mL/min。

关键词：热脱附-气相色谱/质谱联用法；苯系物；气相标准物质；液相标准物质；甲醇

中图分类号: O657.71     文献标识码: A     文章编号：0258-3283（2021）

Difference Effect of Gas or Liquid Phase Standard Reference Material on the Determination of MonoaromaticHydrocarbons in Ambient Air using TD-GC/MS Method

 WEI Wang-hui¹, DONG Yi¹, YU Rui-xiang¹, JIANG Yang¹, REN Yi-chen¹, GAO Yan-qiu¹, CHEN Ying ^{1 *} (Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China)

Abstract：In this work, TD-GC/MS was used to explore the differential influence of gas or liquid phase standard reference material (SRM) on the determination of monoaromatic hydrocarbons in gas samples. The calibration curves of gas and liquid phase SRMs for 7 kinds of monoaromatic hydrocarbons were drawn, and the response of liquid phase SRM was significantly higher than that of the gas phase SRM. Through a series of conjectures and experimental verifications such as penetration teat, re-desorption teat, methanol test, etc., it was believed that the high-energy atmosphere formed by the massive ionization of methanol improves the ionization ability of monoaromatic hydrocarbons and increases the response of the liquid phase target. Therefore, gas phase SRM was more suitable for the quantitative detection of monoaromatic hydrocarbons in gas samples such as ambient air than liquid phase SRM. Lastly, the reliability of the gas phase SRM method was further verified by precision experiments, and the optimal sample collection rate 100mL/min was given.

Key words: Thermal desorption-Gas chromatography/Mass spectrometry; monoaromatic hydrocarbons; gas phase standard reference material; liquid phase standard reference material; methanol

一种新型比率型次氯酸根荧光探针的合成及性能研究

李漫¹，郭洁¹，冯新颖²，周晓华¹，张迪^*1，付博²，王铁良¹

（1. 河南省农业科学院 农业质量标准与检测技术研究所，河南 郑州  450002；2. 河南农业大学 烟草学院，河南 郑州  450002）

摘要：以4-二苯氨基苯甲醛为原料，与水合肼进行缩合反应，设计合成一种识别OCl^-的比率型探针。通过光谱分析，加入OCl^-，荧光发射强度明显升高，溶液颜色由黄色变为无色，实现裸眼识别；加入其他分析物，荧光强度无明显变化。在0.5～1 μmol/L的浓度范围内，荧光强度与次氯酸根浓度呈良好的线性关系，最低检出限为0.44 μmol/L。该检测线满足国家饮用水残氯量的要求，并成功地应用于水的实际样品中检测次氯酸根。

关键词：裸眼识别；次氯酸根；三苯胺；比率；荧光探针

中图分类号：O625       文献标识码：A     文章编号：0258-3283（2021）

Synthesis and Spectral Characterization of Novel Ratiometric Probe of OCl^-

LI Man¹, GUO Jie¹, FENG Xin-ying², ZHOU Xiao-hua¹, ZHANG Di^{* 1}, FU Bo², WANG Tie-liang¹ (1. Institute of Agricultural Quality Standards and Testing Technology, Zhengzhou 450002, China; 2. College of Tobacco Science, Henan Agricultural University, Zhengzhou 450002, China)

Abstract: A probe were synthesized in a easy method from condensation reaction of  4-(diphenylamino)benzaldehyde and hydrazine monohydrate has been synthesized  and used for the ratiometric detection of OCl^-. In this work, the probe exhibited a strong fluorescence enhancement upon addition of OCl^- while showing almost no response to these tested analytes. In the meantime, the solution color obviously changed from yellow to colorless, which showed naked-eye detection of OCl^-. In the range of 0.5-1 μM, the detection limit of probe for the determination of OCl^- was estimated 0.44 μM. The detection limit met residual chlorine of the national drinking water criterion. Moreover, it has been successfully applied to the determination of hypochlorite in water samples.

Key words: naked-eye；OCl^-；triphenylamine；ratiometric；Fluorescence Probe

水溶性弛豫试剂在醇、酸、胺体系中的定量研究

王丹，杨洗，陈杰，张明峰，黄长荣，李晶

（万华化学集团股份有限公司，山东 烟台264006）

摘要：在核磁共振实验中，¹³C核弛豫慢，利用核磁共振¹³C谱对应用体系中的碳核进行定量分析需要耗费大量的实验时间，通常需要在体系中加入顺磁性弛豫试剂，可以有效提高¹³C核的弛豫速率，缩短实验。开发了EDTA-Cu作为弛豫试剂分别应用于不同类型的水溶性样品，研究结果表明EDTA-Cu络合物浓度为0.03～0.04 mol/L时谱图效果最佳，EDTA-Cu的加入不仅不会对醇类、磺酸、羧酸类、叔胺、仲胺样品的谱图效果产生负面影响，而且能在保证缩短实验时间的基础上，提高定量分析的准确性。

关键词：定量碳谱；弛豫试剂；顺磁性离子；EDTA-Cu

中图分类号：O652.3      文献标识码：      A文章编号：0258-3283（2021）

Quantitative Study of Water Soluble Relaxation Reagent in Alcohol, Acid and Amine System

WANG Dan, YANG-xi, CHEN Jie, ZHANG Ming-feng,HUANG Chang-rong, LI Jing (Wanhua Chemical Group Co., Ltd., Yantai 264006,China), HuaxueShiji, 2021, 43(1),     ～

Abstract：Due to the slow relaxation rate of ¹³C atoms, it often needs a long time to quantify in ¹³C NMR analysis. The addition of paramagnetic relaxation reagent can enhance the relaxation rateandreducethe experimental time. Here EDTA-Cu was synthesized as a relaxation reagent for different types of water-soluble samples. The results indicate that the optimal concentration of EDTA-Cu is 0.03～0.04 mol/L.EDTA-Cu has no negative effect on these spectra of alcohols, sulfonic acids, carboxylic acids, tertiary amines and secondary amines. Quantitative¹³C NMR experiments show that the addition of EDTA-Cu can shorten the T1 value of the sample and achieve a better quantitative result on the premise of a shorter D1.

Key words: ¹³C NMR; relaxation reagent; paramagnetic metal ion; EDTA-Cu

响应面法优化花椒叶多糖提取工艺及抑菌活性研究

孙伟，蔡静，叶润^*，赵丽平，王欣

（信阳农林学院 生物与制药工程学院，河南 信阳  464000）

摘要：为确定从花椒叶中提取多糖的最佳工艺条件及其抑菌活性，以花椒叶为原料、蒸馏水为浸提剂，采用超声波辅助提取花椒叶多糖。在单因素实验的基础上，选定料液比为1∶20 g/mL，并进一步选取超声温度、超声时间、醇沉浓度为考察因素，以花椒叶多糖提取率为响应值，应用Box-Behnken试验进行3因素3水平设计，采用响应面法来优化花椒叶多糖的提取工艺，并用牛津杯法对其抑菌作用进行测定。结果显示：料液比1∶20 mL/mg、超声时间38 min、超声温度69 ℃、醇沉浓度为90%条件下，花椒叶多糖提取率最高，实际测得值为0.981%，与理论值0.990%接近。抑菌实验结果显示，花椒叶多糖对金黄色葡萄球菌、大肠埃希氏杆菌和鼠伤寒沙门氏菌均有明显的抑制作用，其中对金黄色葡萄球菌的抑制作用更为明显。说明该工艺参数切实可行，且提取得到的花椒叶多糖具有一定的抑菌作用。

关键词：花椒叶；多糖；超声波；响应面；抑菌活性

中图分类号：O629.3   文献标识码：A     文章编号：0258-3283（2021）

Optimization of the Extraction Technology of Polysaccharides from Chinese Prickly Ash Leaves by Response Surface Method and Its Antibacterial Activity

SUN Wei, CAI Jing, YE Run^*, ZHAO Li-ping, WANG Xin (School of Biology and Pharmaceutical Engineering, Xinyang Agriculture and Forestry University, Xinyang 464000, China), Huaxue Shiji, 2021, 43(1),    ～  

Abstract: The extraction process of polysaccharides from Chinese Prickly Ash leaves was optimized and its antibacterial activitywas evaluated. Polysaccharides was extracted from Chinese Prickly Ash leaves by ultrasonic assisted extraction with distilled water. Preliminary single factor experiments show that ultrasonic temperature, ultrasonic time, alcohol concentration notably altered the extraction efficiency,thus a Box-Behnken second-order polynomial model involving three factors at three levels was developed to investigate the favorable polysaccharide extraction condition, while solid-liquid ratio was fixed as 1:20 g/mL, the bacteriostatic effects was determined by Oxford cup method. The results showed that the extraction rate of polysaccharide from Chinese Prickly Ash leaves was the highest under the conditions of 1:20 (mL/mg) solid-liquid ratio, 38 min ultrasonic time, 69 ℃ ultrasonic temperature and 90% alcohol precipitation concentration. The measured actual value was 0.981%, which was close to the theoretical value 0.990%; The bacteriostatic test results showed that the polysaccharides had obvious inhibitory effect on Staphylococcus aureus, Escherichia coli and Salmonella typhimurium, especially on Staphylococcus aureus. It shows that the process parameters are feasible, and the extracted polysaccharide has a certain bacteriostatic effect.

Key words: Chinese Prickly Ash leaves; polysaccharide; ultrasonic; response surface; antibacterial ability

罗汉果浸膏的提取及其热裂解产物分析研究

黄世杰¹，张文洁²，宋凌勇¹，周芸¹，陈志燕^*1，胡超¹，施怡¹，张峻松²

(1. 广西中烟工业有限责任公司，广西 南宁  530001; 2. 郑州轻工业大学 食品与生物工程学院，河南 郑州  450001)

摘要：为研究罗汉果浸膏的热裂解行为，通过气相色谱-质谱法(GC-MS)分析了罗汉果浸膏挥发性成分，并利用热裂解-气相色谱/质谱联用仪(Py-GC/MS)对罗汉果浸膏进行热裂解研究，对比分析了罗汉果浸膏裂解前后成分的变化。结果表明：罗汉果浸膏的香味成分主要有：糠醛、糠醇、5-甲基糠醛、2,4-二羟基-2,5-二甲基-3(2H)-呋喃-3-酮、5-羟甲基糠醛和反式角鲨烯等。罗汉果浸膏在300 ℃条件下的裂解产物较少，主要为丁醛、异戊醛、乙酸；600、750、900 ℃下的热裂解产物明显增多，较罗汉果原组分、300 ℃下的裂解产物，增加了呋喃类、酮类、烯烃类、含氮杂环化合物、苯系物及一些其他化合物。罗汉果浸膏裂解产物中挥发性成分种类及含量较原组分整体增加，如呋喃类、酮类、烯烃类、含氮杂环化合物等均有所增加，乙酸等有机酸含量较原组分有所下降。

关键词：罗汉果浸膏；香味成分；挥发性成分；热裂解产物；热裂解-气相色谱/质谱联用仪

中图分类号：O656.22     文献标识码：A      文章编号：0258-3283（2021）

Extraction of Siraitia grosvenorii Extract and Analysis of Thermal Pyrolysis Products

HUANG Shi-jie¹, ZHANG Wen-jie², SONG Ling-yong¹, ZHOU Yun¹, CHEN Zhi-yan^*1, HU Chao ¹,SHI Yi ¹, ZHANG Jun-song² (1. China Tobacco Guangxi Industrial Co., Ltd., Nanning 530001, China; 2. College of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China)

Abstract:In order to study the pyrolysis behavior of Siraitia grosvenorii extract, the volatile components of Siraitia grosvenorii extract were analyzed by gas chromatography-mass spectrometry (GC-MS), and the pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) The pyrolysis of Siraitia grosvenorii extract was carried out, and the composition changes before and after the pyrolysis of Siraitia grosvenorii extract were compared and analyzed.The results showed that: (1) The main aroma components of Siraitia grosvenorii extract are: furfural, furfuryl alcohol, 5-methylfurfural, 2,4-dihydroxy-2,5-dimethyl-3(2H)-furan-3-one , 5-hydroxymethyl furfural and trans-squalene.(2) The pyrolysis products of Siraitia grosvenorii extract at 300 ℃ are less, mainly butyraldehyde, isovaleraldehyde, and acetic acid; the pyrolysis products at 600 ℃, 750 ℃ and 900 ℃ were significantly increased, and furans, ketones, olefins, nitrogen-containing heterocyclic compounds, benzenes and some other compounds were added compared with the original components of Siraitia grosvenorii and the pyrolysis products at 300 ℃.(3) The types and contents of volatile components in the pyrolysis products of Siraitia grosvenorii extract increased compared with the original components, such as furans, ketones, olefins, nitrogen-containing heterocyclic compounds, etc., and the content of organic acids such as acetic acid was higher than the original components. The composition has decreased.

Keywords: Siraitia grosvenorii extract; Fragrance ingredients; Volatile components; Thermal cracking products; Py-GC/MS

3-乙酰基香豆素肟衍生物的合成及抗肿瘤活性

尚飞扬，张强，冯贝贝，何黎琴*

（安徽中医药大学 药学院，安徽 合肥  230038）

摘要：以水杨醛为起始原料，经Knoevenagel反应得到3-乙酰基香豆素，将其酮羰基与盐酸羟胺反应得到肟，利用肟羟基与不同碳数的二溴烷烃反应得到相应的溴代肟醚，再与硝酸银反应得到5个3-乙酰基香豆素肟硝酸酯杂合物。目标化合物的结构经过红外光谱、核磁共振氢谱和质谱确证。用检测灵敏度高的CCK-8法评价了目标化合物对人肝癌HepG2细胞、人前列腺癌22RV1细胞、人胃癌HGC-27细胞及人肺癌A549细胞增殖的影响，结果显示，3-乙酰香豆素肟硝氧丁基醚对受试的前3种癌细胞均具有较强的增殖抑制作用。

关键词：癌症；3-乙酰基香豆素；肟醚；硝酸酯；增殖抑制

中图分类号：R916      文献标识码：A         文章编号：0258-3283（2021）

Synthesis and AnticancerActivity of 3-Acety-coumarin Oxime Ethers Derivatives

SHANG Fei-yang, ZHANG Qiang, FENG Bei-bei, HE Li-qin^*(College of Pharmacy, Anhui University of Chinese Medicine, Hefei, Anhui 230038, China)

Abstract: 3-Acetyl-coumarin was obtained from salicylaldehyde and ethyl acetoacetate by the Knoevenagel reaction, which was then treated with NH₂OH to afford 3-acetyl-coumarin oxime. 3-Acetyl-coumarin oxime treated with dibromoalkanes ( 2 ~ 6 carbons) in the presence of K₂CO₃ to provide the compounds 3-acethlcoumarin oxime bromoalkyl ether, these compounds were then reacted with silver nitrate to give the target compounds 3-acety-coumarin oxime ethers derivatives. The chemical structure of target compounds was confirmed  by ¹HNMR, IR, and HR-MS. The in vitro antiproliferative activities of the synthesized compounds were assessed against human cancer cell lines (HepG2, 22RV1, HGC-27 and A549). Among them, compound 4c exhibited od cell proliferation inhibition in HepG2 and HGC-27 cell lines according to the CCK-8 assay.

Key words: cancer; 3-acetyl-coumarin; oxime ethers; nitrate; proliferation inhibition