ZnO基材料室温气体传感性能研究综述

张永辉^*，彭明星，王超楠，巩飞龙

(郑州轻工业大学材料与化学工程学院，河南郑州 450002)

摘要：气体传感器广泛应用于有毒有害气体的监测，在人体健康情况及相关疾病的早期检查和预防中也具有良好的应用前景。ZnO由于具有制备方法简单，来源广泛，优异的n型半导体特性等优点被认为是最有前景的气体传感材料之一。然而ZnO基气体传感器在室温下低的氧化还原反应速率，对检测气体较差的吸附反应活性限制了其在室温下的应用。近年来研究人员就如何提高ZnO基气体传感器在室温下的传感性能进行了深入的探索并取得一定的成果。基于此，对形貌调控、掺杂和光激发等提高ZnO气体传感器室温传感性能的策略做出了综述并进一步提出了存在的问题和未来的发展方向。

关键词：ZnO；室温；形貌调控；掺杂；光激发

中图分类号：O614  文献标识码：A  文章编号：0258-3283（2021）--

Room Temperature Sensing Strategies for ZnO-based Gas Sensors: A Review

ZHANG Yong-hui^*, PENG Ming-xing, WANG Chao-nan, NG Fei-long (School of Material and Chemical, Zhengzhou University of Light Industry, Zhengzhou 450002, China), Huaxue Shiji, 2021, 43(3), ～

Abstract: Gas sensors are widely used in monitoring toxic and harmful gases, and present numerous prospects in the application of previous detection and prevention of human health conditions. Due to the simple synthesis method, wide range of sources and excellent n-type semiconductive properties, ZnO is considered to be one of the most promising gas sensing materials. However, the relatively low redox reaction rate of the ZnO-based gas sensor derived from the poor adsorption reaction activity hinders its application at room temperature. In recent years, researchers have made extensive explorations to improve the sensing performance of ZnO-based gas sensors at room temperature, and achieved exciting advances. In this work, the strategies including morphological regulation, doping, light excitation and other measures to improve the sensing performance of ZnO at room temperature were summarized, and the issue at present and the developing tendency in the future was also proposed.

Key words: ZnO; morphology; room temperature; doping; photoexcitation

CoPc/N-C催化剂的制备及CO₂电催化还原

马静静，朱红林^*

（宁波大学 材料科学与化学工程学院 化学合成与绿色应用研究所，浙江 宁波  315211）

摘要：金属酞菁（MePcs）因其易得性和结构可调性被认为是一种很有前途的CO₂减排催化剂。其中，酞菁钴（CoPc）基杂化材料用于电催化CO₂还原（CO₂-RR）近年来受到了广泛关注。通过制备简便的2-甲基咪唑锌盐MOF材料为前驱体，N₂气氛下热解后的N-C作为载体，在DMF的超声作用下与CoPc混合制备CoPc/N-C。在三电极体系下，0.1 mol/L KHCO₃电解液中，CoPc/N-C表现出较好的CO₂电催化还原为CO的性能，过电位低至190 mV，在电位-0.7～-1 V vs RHE电势区间表现出较高的CO法拉第效率（>85%）且具有较好的稳定性，其优异的电催化CO₂还原性能主要归因于复合材料中CoPc与N-C载体之间的协同作用。

关键词：金属酞菁；酞菁钴；电化学CO₂还原；杂化材料；金属有机骨架

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

Preparation of CoPc/N-C Catalyst and Electrochemical Reduction of CO₂

MA Jing-jing, ZHU Hong-lin^* (Institute of Chemical Synthesis and Green Applications, College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China), Huaxue Shiji, 2021, 43(3)

Abstract:Metal phthalocyanines (MePcs) have been considered as promising catalysts for CO₂ emission reduction due to accessibility and structural tunability. Among them, cobalt phthalocyanine (CoPc) based hybrid material for electrocatalytic CO₂ reduction (CO₂-RR) has received extensive attention in recent years. Herein, CoPc/N-C was prepared by mixing CoPc under ultrasonic of DMF with N-C carrier which was pyrolyzed via 2-methylimidazole zinc salt MOF material as the precursor under N₂ atmosphere. In a three-electrode system, the CoPc/N-C exhibits excellent performance for reducing CO₂ to CO with low overpotential 190 mV, Faraday efficiency of CO (FE_CO) exceeded 85% over a wide potential range from -0.7～-1 V vs RHE and remarkable stability in the 0.1 mol/L KHCO₃ electrolyte. The excellent electrocatalytic performance could be obtained due to the synergistic effect on the interface of CoPc and N-C.

Key words: metal phthalocyanine; cobalt phthalocyanine; electrochemical CO₂ reduction; hybrid materials; MOF

Na₂CO₃、K₂CO₃和KOH制备废弃柑橘皮渣活性炭及其性能分析

张晓凤^*1，项锦欣²，田井清²，谢燕²

（1. 重庆科技学院 电气工程学院，重庆 401331；

2. 重庆理工大学 化学化工学院，重庆 400054）

摘要：随着柑橘加工业的发展，柑橘皮渣后续处理问题日益突出，废弃柑橘皮渣成为亟待解决的农业废弃物，将其制备成柑橘皮渣活性炭是非常有意义的，而活化剂的选择是制备高吸附性能活性炭的关键。以废弃柑橘皮渣为原料，利用活化剂类型、浸渍比和活化温度3个关键因素，探究了Na₂CO₃、K₂CO₃和KOH这3种活化剂对制备柑橘皮渣活性炭产率与吸附性能的影响，利用比表面积与孔容、红外光谱、扫描电镜和能谱分析表征了3种活化剂对柑橘皮渣活性炭孔隙结构、表面功能基团、形貌与微区元素组成分析的影响，深入解析了3种活化剂在制备柑橘皮渣活性炭时活化作用的差异，为制备高性能柑橘皮渣活性炭提供理论依据。结果表明，以Na₂CO₃为活化剂制备的柑橘皮渣活性炭性能最佳。

关键词：废弃柑橘皮渣；活性炭；活化剂；活化作用；表征

中图分类号：TQ 424.1  文献标志码：A  文章编号：0258-3283（2021）--

Preparation of Activated Carbons from Waste Citrus Dregs by Na₂CO₃, K₂CO₃ and KOH and Performance Analysis

ZHANG Xiao-feng^*1, XIANG Jin-xin², TIAN Jing-qing², XIE Yan² (1. School of Electrical Engineering, Chongqing University of Science＆Technology, Chongqing 401331, China; 2. College of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China), Huaxue Shiji, 2021, 43(3), ～

Abstract: Waste citrus peel dregs is an urgent need to solve agricultural waste. It is significant to prepare activated carbon from waste citrus peel dregs. The choice of activator is the key to prepare activated carbon with high adsorption property. The activated carbons were prepared from waste citrus dregs by chemical activation, while Na₂CO₃, K₂CO₃ and KOH were used as chemical activation agents. The appropriate parameters of waste citrus dregs based activated carbons prepared were investigated by taking three key factors including different impregnation agents, impregnation ratio and activation temperature. The effects of activators type on the yield and adsorption properties of activated carbon were investigated. In order to analyze the influence of three activators on the pore structure, surface functional groups, morphology and microzone element composition analysis of activated carbon, characterization techniques such as automatic specific surface area and pore size analyzer, transform infrared spectrometer(FTIR) and scanning electron microscope and energy dispersive spectrometer(SEM-EDS) were used. The difference of activation effect for various activators on waste citrus dregs was analyzed. It provides theoretical basis for the preparation of high performance citrus dregs activated carbon. The citrus peel activated carbon had the best performance when Na₂CO₃ was used as activator.

Key words: waste citrus dregs; activated carbons; activator; activation; characterization

以月神为名的元素：硒的应用与展望

钱蓉蓉¹，俞磊^*2

（1. 江苏旅游职业学院，江苏 扬州  225127；

2. 扬州大学 化学化工学院，江苏 扬州  225002）

摘要：硒（Selenium）得名于古希腊神话中的月神赛勒涅（Selene），是一种硫属准金属元素。最近十年以来，硒科学研究蓬勃发展。除了传统的硒化学研究之外，含硒化合物与材料在多个学科领域的研究中也发挥了重要的作用。硒化学与其它学科的交叉发展，是一个重要的发展趋势，也要求科研人员具备更广阔的学术视野。本文围绕含硒化合物与材料在合成化学、催化化学、环境保护、农业化学品等方面的应用展开论述，并提出开发专用硒化试剂，以降低由于合成含硒化合物与材料需要较高合成技巧所带来的技术壁垒的发展思想，希望能对相关研究者有所帮助。

关键词：硒；合成；催化；环境保护；农业

中图分类号：O6  文献标识码： A  文章编号：0258-3283（2021）

Element Named Based on d of Moon: Application and Prospect of Selenium

QIAN Rong-rong¹, YU Lei^*2 (1. Jiangsu College of Tourism, Yangzhou 225127, China; 2. School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China), Huaxue Shiji, 2021, 43(3)

Abstract: The name of selenium comes from Selene, the d of moon in ancient Greek mythology. It is a chalcogen metalloid element. During the last decade, the investigations on the science of selenium are booming. Besides the traditional investigation on selenium chemistry, the selenium-containing compounds and materials play important roles in the investigations in multiple disciplines. The interdisciplinary development of selenium chemistry and other disciplines is an important development trend, and it requires broader academic visions of the investigators. In this work, the applications of selenium-containing compounds and materials in synthetic chemistry, catalysis chemistry, environment protection and agricultural chemicals were discussed. It was suggested that developing the special selenization reagent could reduce the technical barriers caused by the need for higher synthesis skills in the synthesis of selenium-containing compounds and materials, and this idea might be helpful for the related investigators.

Key words: Selenium; synthesis; catalysis; environment protection; agriculture

衍生化气相色谱法检测化学毒剂相关化合物的试剂和方法进展

魏佳楠，杨俊超，秦墨林，李宝强，杨柳^*

（国民核生化国家重点实验室，北京  102205）

摘要：化学毒剂是高毒性的危险化学物质，时至今日仍然对人类和社会具有潜在威胁。化学毒剂及其降解产物的分析是验证化学毒剂存在的重要方法。气相色谱法以及气相色谱-质谱联用法是用于检测相关化合物的主要技术。由于许多化学毒剂的水解、降解产物具有极性大、难挥发的特点，因此需要通过衍生化试剂进行反应成为挥发性高，低极性、低反应性的便于色谱分析的物质。综述近15年来气相色谱衍生化法检测化学毒剂水解、降解产物等相关化合物的研究进展，列表对比了包括新的衍生化试剂的方法和衍生条件，分析了新的衍生化试剂开发的趋势。对于开展相关化合物的衍生化气相色谱分析研究工作进行了评述。

关键词：化学毒剂；气相色谱；衍生化试剂；衍生化方法

中图分类号：O652.6; X592  文献标识码：A  文章编号：0258-3283（2021）

Development of Reagents and Methods for Detection of Chemical Warfare Agents Related Compounds by Derivatization-gas Chromatography Method

WEI Jia-nan, YANG Jun-chao, QIN Mo-lin, LI Bao-qiang, YANG Liu^*（State Key Laboratory of NBC Protection for Civilian, Beijing 102205, China）, Huaxue Shiji, 2021, 43(3)

Abstract：Chemical warfare agents （CWAs) are extremely toxic chemicals that still pose a potential threat to humans and society today. The analysis of chemical warfare agents and their degradation products is an important methods of verify the existence of them. Gas chromatography (GC) and Gas chromatography-mass spectrometry (GC-MS) are the major techniques used to detect and identify CWAs and related compounds. Generally, CWA hydrolysis products are much more polar and less volatile han CWAs. The major need for derivatisation is for the analysis of polar hydrolysis products of CWAs. Polar hydrolysis products are usually derivatized to facilitate chromatography and to impart properties beneficial for detection. The research progress of GC derivatization method for detecting the hydrolysis and degradation products of CWAs in the past fifteen years were introduced in this work. Different derivatization conditions and derivatization reagents were summary in this article. Finally, the future development for derivatization reagents and methods in CWAs detection are also discussed along with perspectives.

Key words: chemical warfare agent; gas chromatography; derivatization reagent; derivatization method

手性吡啶单噁唑啉配体在不对称催化反应中的研究进展

张文杰，曹国锐^*

（青岛科技大学 化工学院，山东 青岛  266042）

摘要：手性吡啶单噁唑啉配体是一类双氮配位，易与钯、铑、铱等多种金属络合，具有结构简单、价格低廉的优点。手性吡啶单噁唑啉配体中的吡啶环以及噁唑啉环上均具有丰富的修饰位点，可协调配体与底物之间的适应性，使反应更加快捷高效，在不对称催化领域涌现出丰富的科研成果。综述了近20多年关于手性吡啶单噁唑啉配体在共轭加成反应、Heck偶联反应、Aza-Wacker反应、C—H官能团化反应等不对称催化反应中的应用，并对手性吡啶单噁唑啉配体的应用前景进行了展望。

关键词：吡啶单噁唑啉配体；共轭加成反应；Heck偶联反应；Aza-Wacker反应；C—H官能团化反应

中图分类号：O621.1  文献标识码：A  文章编号：0258-3283（2021）

Progress of Chiral Pyridine Monooxazoline Ligands in Asymmetric Catalytic Reactions

ZHANG Wen-jie, CAO Guo-rui^*(College of Chemistry Engineering, Qingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2021, 43(3)

Abstract: Chiral pyridine monoxazoline ligands are a kind of diazo coordination ligands, which tend to complex with palladium, rhodium, iridium and other metals, and have the advantages of simple structure and low price. Both the pyridine ring and the oxazoline ring in the chiral pyridine monooxazoline ligand have abundant modification sites, which can coordinate the adaptability between the ligand and the substrate, making the reaction faster and more efficient. And rich scientific research achievements have emerged in the field of asymmetric catalysis. The applications of chiral pyridine monoxazoline ligands in asymmetric catalytic reactions such as conjugated addition reaction, Heck coupling reaction, Aza-Wacker reaction and C—H functionalization reaction were reviewed in the past 20 years, and the application prospect of chiral pyridine monoxazoline ligands was prospected.

Key words：pyridine monooxazoline ligand; conjugation addition reaction; Heck coupling reaction; Aza-Wacker reaction; C—H functionalization reaction

吡唑啉类荧光探针的设计与应用研究进展

曹碧霞¹，韩正枝²，刘荣^*1

(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)

摘要：吡唑啉基团具有较强的蓝光发射，高的荧光量子产率及空穴传输效率，可以作为优质荧光基团参与荧光探针的设计与合成，此外，其结构中存在含孤对电子的N原子，因此也可做为识别基团承担提供结合位点的重要作用。近年来，利用吡唑啉基团的上述特点来设计合成性能优良的荧光探针已成为荧光探针研究领域中瞩目的焦点，综述了近年来具有代表性的吡唑啉类荧光探针在各种金属离子以及二氧化硫、生物硫醇、肼等小分子检测中的应用进展，并展望了其未来的发展趋势。

关键词：吡唑啉；荧光探针；设计；检测；进展    

中图分类号：O65  文献标识码：A  文章编号：0258-3283（2021）--

Progress in Design and Application of Pyrazoline-based Fluorescent Probes

CAO Bi-xia¹, HAN Zheng-zhi², LIU Rong^* (1. Gansu Research Institute of Chemical Industry Co., Ltd., Lanzhou 730020, China; 2. Gansu Key Laboratory of Fine Chemicals, Lanzhou 730020, China), Huaxue Shiji, 43(3), ～

Abstract: Pyrazoline group has excellent blue light emission, high fluorescence quantum yield and hole-transporting efficiency, so it can be used as a high-quality fluorophore to design and synthesis fluorescent probes. In addition, pyrazoline group also contains nitrogen atom with a lone pair of electrons, so it is also viewed as recognition group to play an important role on binding sites. Recently, utilizing these properties of pyrazoline group to design and synthesis better fluorescent probes has gradually become one of focuses in fluorescent detection research. Therefore, this article reviews the application progress of representative pyrazoline fluorescent probes in the detection of various metal ions and small molecules such as sulfur dioxide, biological thiols, and hydrazine in recent years, and their development tendency in the future is prospected.

Key words：pyrazoline; fluorescent probe; design; detection; progress

危险化学品储存及其数量规制的现状与困境

宋金链，杜文玲^*，郭培，张键鑫，李润喜

（天津市康科德科技有限公司，天津  301701）

摘要：选取具有代表性的法律、法规和标准对危险化学品储存及其数量的相关规定进行分析。通过分析可见，法律法规主要阐述危险化学品储存的安全规定，大都是根据危险化学品的性质进行规定，并未对危险化学品储存的数量、方法给出具体要求；在数量管控方面，法律法规中对构成重大危险源的危险化学品进行了规定，也提到了民用小包装的危险化学品存放要求，但是对于未构成重大危险源的工业小包装、少量化学试剂的储存并未作具体要求。这使得科学研究、教学、药物研发、医疗、实验中少量危险化学品的管理和使用面临两难的困境，已逐渐影响到科学实验和研发工作的深入开展，应该高度重视并找出科学合理的解决办法，推动危险化学品依法监管、理性监管和科学管理水平。

关键词：储存；危险化学品；规制；数量；现状；困境

中图分类号：O6-1  文献标识码：A  文章编号：0258-3283（2021）

Current Situation and Challenges of Regulations on Storage and Quantity of Hazardous Chemicals

SONG Jian-lian, DU Wen-ling^*, GUO Pei, ZHANG Jian-xin, LI Run-xi (Tianjin Concord Technology Co., Ltd., Tianjin 301701, China), Huaxue Shiji, 43(3),

Abstract: We analyzed representative laws, regulations and standards on storage and quantity of hazardous chemicals in this paper. Our analysis showed that current laws and regulations mainly elaborated the safety provisions of the storage of hazardous chemicals, but failed to provide specific requirements for the quantity and methodology of hazardous chemicals storage. In terms of quantity control, regulations have been imposed on the hazardous chemicals that constitute the major hazard installations and the storage requirements of hazardous chemicals in small packages for civil use. However, currently there are no regulations for the storage of hazardous chemicals in small packages for industrial use or small quantities of chemical reagents that do not constitute major hazard installations. This makes the management and usage of small amounts of hazardous chemicals inconvenient for scientific research, teaching, drug research and development and medical treatment, which has gradually affected the development of scientific studies. Therefore, we should prioritize finding scientific and reasonable solutions to such problems.

Key words: storage; hazardous chemicals; laws and regulations; quantity; present situation; dilemma

化学试剂储存有限数量包装安全监管豁免研究

宋金链，刘岩^*，张键鑫，郭培

（天津市康科德科技有限公司，天津  301701）

摘要：化学试剂是科学研究的重要基础耗材，对多个学科的整体发展起关联推动作用。当前对于化学试剂的监管考虑性质多，综合考虑性质、数量、场景、措施的少，有必要根据《危险化学品重大危险源辨识》中的辨识指标确定不同性质和数量危险化学品的相对危险性，借鉴《危险货物道路运输通则》，探讨制定化学试剂储存有限数量包装的基本条件，制定化学试剂储存有限数量包装，进行监管豁免。本文通过对危险化学品的临界量、危险货物有限数量包装、危险货物有限数量包装的辨识指标的情况分析，为化学试剂科学监管提出了制定化学试剂有限数量包装，确定安全监管豁免依据的标准。

关键词：化学试剂储存；安全监管豁免；有限数量包装；临界量；危险源辨识

中图分类号：O6-1  文献标识码：A  文章编号：0258-3283（2021）

Research on Exemption of Safety Supervision of Limited Quantity Packaging for Chemical Reagents Storage

SONG Jin-lian, LIU Yan^*, ZHANG Jian-xin, GUO Pei (Tianjin Concord Technology Co., Ltd., Tianjin 301701, China), Huaxue Shiji, 43(3),

Abstract: Chemical reagent is an important consumable for scientific research, which is key to development of multiple disciplines. At present, most of the regulations on chemical reagents consider only the chemical properties of the reagents and ignore other factors such as quantity, scenario and measures. Therefore it is necessary to determine the relative hazard level of dangerous chemicals of different properties and quantities according to the identification indicators in "Identification of major hazard installations for dangerous chemicals" and explore the basic conditions of limited quantity packaging for chemical reagents storage, regulate the limited quantity packaging for chemical reagents storage and implement regulatory exemptions accordingly, by referencing "Regulations concerning road transportation of dangerous ods". This paper proposes a scientific standard for the limited quantity packaging for chemical reagents storage and the conditions for exemptions of safety supervision, by analyzing the critical quantity of dangerous chemicals, limited quantity packaging for dangerous chemical reagents storage, and its current standards.

Key words: chemical reagents storage; safety supervision exemption; limited quantity packaging; critical quantity; hazard identification

龙葵吸附重金属镉的生物有效性的研究

邹继颖¹，胡良宇²，刘辉^*1，孙彩云¹，李健炜¹，吕逸寒¹，权佳惠¹，李万海¹

（1. 吉林化工学院 资源与环境工程学院，吉林 吉林  132022；

2. 安徽理工大学 地球与环境学院，安徽 淮南  232001）

摘要：选取龙葵及种植龙葵的土壤作为研究对象，测定土壤中重金属镉的含量、土壤重金属可交换态镉、碳酸盐结合态镉、铁锰氧化物结合态镉、有机结合态镉、残渣态镉的化学形态含量，同时测定土壤的阳离子交换量、比重、pH等，并分析了土壤中不同化学形态的重金属镉的分布特征，同时分析影响重金属镉形态分布及生物有效性的因素。结果表明，土壤重金属镉化学形态的分布规律受到重金属全量、土壤理化性质以及龙葵的生长环境的影响，其中在自然环境种植龙葵土壤中和模拟种植龙葵土壤中，其转化系数与土壤重金属镉全量之间均呈显著负相关；在二次加入外源镉的土壤中，其转化系数与土壤重金属镉全量之间呈极显著负相关。土壤重金属镉的生物有效性主要通过生物可利用系数、迁移系数及转化系数来反映，三者均受龙葵的生长环境和土壤重金属中镉全量的影响。

关键词: 重金属；镉；龙葵；化学形态；生物有效性

中文分类号：X43      文献标识码：A      文章编号：0258-3283（2021）--

Effect Factors of Cd Bioavailability Adsorped by Solanum Nigrum L.

ZOU Ji-ying¹, HU Liang-yu², LIU Hui^*1, SUN Cai-yun¹, LI Jian-wei¹, LV Yi-han¹, QUAN Jia-hui¹, LI Wan-hai¹ (1. Department of Resource and Environmental Engineering, Jilin Institute of Chemical Technology College, Jilin 132022, China; 2. Mining and Safety Engineering School, Anhui University of Science and Technology university, Huainan 232001, China), Huaxue Shiji, 43(3), ～

Abstract：The contents of heavy metal cadmium, exchangeable cadmium, carbonate bound cadmium, iron manganese oxide bound cadmium, organic bound cadmium and residual cadmium in Solanum nigrum L. and the soil planted with Solanum nigrum L. were determined. At the same time, the cation exchange capacity, specific gravity and pH of soil were determined, and the heavy metals in soil with different chemical forms were analyzed. Meanwhile, the factors affecting the speciation distribution and bioavailability of cadmium were analyzed. The results showed that the distribution of cadmium in soil was affected by the total amount of heavy metal, the physical and chemical properties of soil and the growth environment of Solanum nigrum L.. In the soil planted with Solanum nigrum L. in the natural environment and in the soil planted with Solanum nigrum L., the conversion coefficient was negatively correlated with the total amount of cadmium in the soil; In the soil with secondary exogenous cadmium, the transformation coefficient was significantly negatively correlated with the soil. There was a significant negative correlation between the total amount of Cd in soil. The bioavailability of soil heavy metal cadmium is mainly reflected by bioavailability coefficient, migration coefficient and conversion coefficient, which are affected by Solanum nigrum L. growth environment and the total cadmium content in soil.

Key words: heavy metal; Cadmium; Solanum nigrum L.; chemical feature; bioavailability

超临界CO₂萃取柏叶油及成分分析

董振山，张欣敏，李德裕，农怀园，夏永明^*

(广西中烟工业有限责任公司, 柳州卷烟厂，广西 柳州  545000）

摘要：采用超临界CO₂萃取柏叶油，通过单因素实验考察萃取条件对萃取率的影响，通过正交试验可知，柏叶油最佳的工艺条件为：萃取压力35 MPa、萃取温度35 ℃、CO₂流量20 L/h、萃取时间2.0 h。采用气相色谱质谱对其成分进行分析，结果共检测出柏叶油70种成分，其中烃类31种、酯类14种、酮类9种、醇类8种。柏油叶中萜烯类物质有18种，质量分数为18.65%。可为柏叶油开发和合理使用提供理论指导。

关键词：超临界CO₂萃取；柏叶油；气相色谱-质谱；单因素试验

中图分类号：TS41  文献标识码：A  文章编号：0258-3283（2021）--

Supercritical CO₂ Extraction and Composition Analysis of Cypress Leaf Oil

DONG Zhen-shan¹, XIA Yong-ming^*1 (1. Guangxi China Tobacco Industry Co., Ltd., Liuzhou Cigarette Factory Liuzhou, Liuzhou 545000, China), Huaxue Shiji, 2021, 43(3)

Abstract: Supercritical CO₂ was used to extract cypress oil, and the influence of extraction conditions on the yield was investigated by single factor experiments. Based on orthonal experiments, the optimal process conditions for cypress oil are: pressure 35 MPa, extraction temperature 35 ℃, extraction time 2 h, the extraction flow rate 20 L/h. The components are analyzed by gas chromatography mass spectrometry. A total of 70 components have been detected, including 31 hydrocarbons, 14 esters, 9 ketones, and 8 alcohols. Among them, there are 18 kinds of terpenes with a mass fraction of 18.65%. This work provides guidance for the development and rational use of cypress oil.

Key words: supercritical CO₂ fluid extraction; cypress leaf oil; GC-MS; single factor test

大气颗粒物中多环芳烃物质检测方法优化研究

张丹¹，魏鑫²，朱宝余¹，孙成勋^*1

（1. 国网吉林省电力科学研究院，吉林 长春  130021；2. 吉林建筑大学 市政与环境工程学院，吉林 长春  130118）

摘要：在探讨不同体系多环芳烃测试方法的基础上，为着重优化大气颗粒物中多环芳烃物质的超声—GC-MS检测分析方法，设置A、B、C、D、E 5组不同萃取剂与超声时间的前处理方法（A= V（二氯甲烷）∶V（丙酮）=1∶1（45 min），B= V（二氯甲烷）∶V（甲醇）=2∶1（60 min），C=正己烷（60 min），D=正己烷（30 min），E= V（丙酮）∶V（正己烷）=1∶1（60 min），处理后的样品利用GC-MS进行测试，结果表明，E组的平均回收率为67.27%～128.59%，相对偏差为0.40%～8.87%，方法最优。同时采用E组方法对2017年10月25日-11月30日（采暖期）和2018年3月19日-4月30日（非采暖期）TSP中16种多环芳烃的含量进行检测分析，得到采暖期和非采暖期含量分别为1.4630×10^-3 μg/mL和1.0951×10^-3 μg/mL，均未超过标准（GB 3095—2012）限值，采暖期与非采暖期中16种多环芳烃中BaP对TEQ的贡献值最大分别为5.61×10^-5 μg/mL（占45.90%）、2.75×10^-5 μg/mL（占34.55%），其次是BbF贡献值分别为2.61×10^-5 μg/mL（占21.36%）、1.94×10^-5 μg/mL（占24.40%），表明BaP和BbF是评价长春市TSP中多环芳烃健康风险的重要组分。

关键词：多环芳烃；超声提取法；GC-MS法；TSP；回收率

中图法分类号：O657.6  文献标识码：A  文章编号：0258-3283（3283）--

Optimization of Detection Methods for PAHs in Atmospheric Particles

ZHANG Dan¹, WEI Xin², ZHU Bao-yu¹, SUN Cheng-xun^*1 (1. State Grid Jilin Electric Power Research Institute, Changchun 130021, China; 2. School of Municipal and Environment Engineering, Jilin Jianzhu University, Changchun 130118, China), Huaxue Shiji, 2021, 43(3), ～

Abstract: On the basis of discussing the testing methods of polycyclic aromatic hydrocarbons in different systems, the work focuses on optimizing the ultrasonic extraction and GC-MS detection and analysis method of polycyclic aromatic hydrocarbons in atmospheric particles. The ultrasonic extraction method was used to set the pretreatment methods for the five groups of different extractants and ultrasonic time (A = dichloromethane: acetone (1∶1) + 45 min, B = dichloromethane: methanol (2∶1) + 60 min, C = n-hexane + 60 min, D = n-hexane + 30 min, E = acetone: n-hexane (1∶1) + 60 min), the processed samples were tested by GC-MS, the results showed that the standard curves of different polycyclic aromatic hydrocarbons in the five groups of schemes were all between 0.993～1.000, the average recovery rate of group E was 67.27%～128.59%, and the relative deviation was 0.40%～8.87%, which was the best method. Using group E method to detect and analyze the content of 16 polycyclic aromatic hydrocarbons in TSP from October 25th to November 30th (heating period) and March 19th to April 30th (non-heating period) in 2018. The contents in heating and non-heating periods were 1.4630×10^-3 μg/mL and 1.0951×10^-3 μg/mL, respectively, which did not exceed the standard (GB 3095—2012) limits. The contribution of BaP to TEQ among the 16 polycyclic aromatic hydrocarbons during heating and non-heating periods were 5.61×10^-5 μg/mL (45.90%) and 2.75×10^-5 μg/mL (34.55%), followed by BbF contribution of 2.61×10^-5 μg/mL (21.36%), 1.94×10^-5 μg/mL (24.40%), indicating that BaP and BbF played an important role in human health risk assessment.

Key words: polycyclic aromatic hydrocarbon; ultrasonic extraction; GC-MS; TSP; recovery rate

超高效液相色谱-三重四极杆质谱法测定化妆品中环吡酮胺含量

李晓宇¹，曹海荣²，王思怿^*1

（1. 上海化工研究院有限公司，上海 200062；2.上海应用技术大学 化学与环境工程学院，上海 201418）

摘要：建立了一种超高效液相色谱-串联质谱（UPLC-MS/MS）的方法用来测定化妆品中环吡酮胺的含量。方法：使用沃特世超高液相色谱 C18色谱柱（1.7 μm×2.1 mm×50 mm），以V（甲醇）∶V（水（含0.1% 甲酸））溶液为流动相进行梯度洗脱，流速设定为0.5 mL/min，进样量设置为2μL，在电喷雾正离子模式下（ESI⁺），采用多反应监测（MRM）模式进行定性和定量。结果表明，建立的分析方法在所研究的浓度范围内浓度和峰面积具有良好的线性关系，相关系数为0.9996，平均加标回收率为107.9%（n=3），平均相对标准偏差（RSD）为4.80%（n=6），检出限浓度为0.0668 mg/kg，定量限浓度为0.223 mg/kg，方法方便、灵敏、准确，适用于化妆品中环吡酮胺的含量检测与质量监督。

关键词：环吡酮胺；化妆品；超高效液相色谱-串联质谱法；检出限；定量限；线性相关系数

中图分类号：O657.63  文献标识码：A  文章编号：0258-3283（2021）--

Determination of Ciclopirox Olamine in Cosmetics by Ultra Performance Liquid Chromatography-triplequadrupole Mass Spectrometry

LI Xiao-yu¹, CAO Hai-rong², WANG Si-yi^*1

(1. Shanghai Research Institute of Chemical Industry Co., Ltd, Shanghai 200062, China; 2. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China), Huaxue Shiji, 2021, 43(3), ～

Abstract: An analytical method for the determination of ciclopirox olamine in cosmetic samples has been developed. The UPLC separation was carried out on a Waters Acquity UPLC? BEH C18 column (1.7 μm×2.1 mm×50 mm) by gradient elution using methanol/water (containing 0.1% formic acid) system. The flow rate is 0.5 mL/min and sample injection amount is 2 μL. The electrospray ionization source in positive ion mode (ESI⁺) was used for qualitative analyzing and quantitative analyzing of ciclopirox olamine in the multiple reaction monitoring (MRM) mode. The developed method has a od linear relationship between concentration and peak area in the corresponding concentration range. The linear correlation coefficient is 0.9996, and the average recoveries of standard addition is 107.9% (n = 3), and the average relative standard deviation is 4.80%(n = 6), the limit of detection is 0.0668 mg/kg, and the limit of quantification is 0.223 mg/kg. The method is convenient, sensitive and accurate, and the od analytical features of the proposed method make it useful to carry out the quality control of cosmetic products and raw materials to assure the safety of users.

Key words: ciclopirox olamine; cosmetics; UPLC-MS/MS; limit of detection; limit of quantification; linear correlation coefficient

海水淡化过程中硼的快速测定方法

王翠翠^*，李艳苹，刘小骐，潘献辉

(自然资源部 天津海水淡化与综合利用研究所，天津  300192)

摘要：运用姜黄素分光光度法，建立了同校准曲线下海水和淡化产水中硼含量同时测定的分析方法。方法采用了静置分离法消除海水盐度基体的干扰，当静置时间达到6 min后，盐度的干扰基本被消除。研究结果表明，硼的浓度在0.10～2.50 μg/mL范围内，校准曲线的相关系数可达0.9999，该分析方法的检出限为0.033 μg/mL，测定下限为0.066 μg/mL，精密度测定结果的相对标准偏差均小于2.5% (n=10)。对来自天津、以色列近岸的两份海水和其各自的淡化产水，以及测定下限附近的浓度样品进行测定，加标回收率为92.3%～104%，其测定结果的准确度满足方法学的技术要求。方法简便、准确度高，适用于海水淡化现场相关水样中硼含量的快速测定。

关键词：硼；姜黄素分光光度法；海水淡化；现场测定

中图分类号：O65  文献标识码：A  文章编号：0258-3283（2021）

Rapid Determination of Boron in Seawater Desalination Progress

WANG Cui-cui^*, LI Yan-ping, LIU Xiao-qi, PAN Xian-hui (The Institute of Seawater Desalination and Multipurpose Utilization, MNR(Tianjin), Tianjin 300192, China), Huaxue Shiji, 2021, 43(3)

Abstract: A method for simultaneous determination of boron in seawater and product water of desalination under the same calibration curve was established with curcumin spectrophotometric method. In the method, the interference of seawater salinity was eliminated with sedimentation. When the sedimentation time reached 6 min, the interference of salinity could be eliminated effectively. The linear correlation coefficient was 0.9999 in the range of 0.10 ~ 2.50 μg/mL. The detection limit of method was 0.033 μg/mL, and the limit of determination was 0.066 μg/mL. The relative standard deviation of the precision measurement results were all less than 2.5% (n=10). Seawater samples were collected from Tianjin and Israel coastal areas, respectively. Concentrations of boron in the samples and product water of desalination were determined. Moreover, the concentration sample near by the limit of determination was also determined. The recoveries were 92.3% ~ 104%, which accuracy was in accordance with the technical requirements of the methodology. The method was easy to operate, and had high accuracy, which could be developed for on-site rapid determination in the seawater desalination process.

Key words: boron; curcumin spectrophotometric method; seawater desalination; on-site determination

室内空气TVOC检测用混合标准气体的制备及性能研究

杨静,杜健,李宁,高冰,倪才倩^*

（生态环境部 环境发展中心环境标准样品研究所

国家环境保护污染物计量和标准样品研究重点实验室，北京  100029）

摘要：采用液态组分气化填充装置，以称量法制备了浓度水平为1 μmol/mol的氮气中9种VOCs混合标准气体，其组分涵盖了《室内空气质量标准》中TVOC检测指标。研究建立气相色谱-氢火焰离子化检测器分析方法对包含的组分进行分离分析。通过制备方法的重复性评估和不同种类型的国产气瓶筛选，确定了采用重量法和II型镀层气瓶可以满足制备本标准气体要求。此外，采用均匀性和稳定性实验考察了制备标准气体的性质。最终，将制备的标准气体与有证气体标准样品进行比对，确认其量值准确、可靠。该标准气体可以为环境监测站、检测机构和科研机构等在相关研究过程中质量控制和质量保证的技术基础。

关键词：室内空气质量；气体标准样品；苯系物；正十一烷；乙酸丁酯

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

Development of TVOCs Gas Standard for Indoor Air Quality Monitoring

YANG Jing, DU Jian, LI Ning, GAO Bing, NI Cai-qian^* (Institute for Environmental Reference Materials, State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Beijing 100029, China), Huaxue Shiji, 2021, 43(3)

Abstract: A gas standard mixture containing 9 volatile organic compounds (VOCs) was prepared using gravimetric method and a gasifying apparatus developed in-house. The components of the gas standard cover the TVOC measurement indicators of 《Indoor air quality standard》. The concentration of each component was determined using a gas chromatograph with flame ionization detection (GC-FID). The weighing method and II-type coating cylinder were proved to be applicable by assessment of the preparation method and selection of cylinder. Also, the stability at different pressures and time were examined. Finally, comparison test with certified reference material was performed to ensure accurate valve.

Key words: indoor air quality; gas standard; benzene series; n-undecane; butyl acetate

浊度计量比对样品的研制

高旭辉^*，黄金梅，李域，常梅，龚敏珍

（陕西省计量科学研究院，陕西 西安 710065）

摘要：按照国际标准要求制备了浊度计量比对样品，其标称值可以溯源至国家一级标准物质，不确定度U=3.2%（k=2），样品均匀性好，在150天内保持量值稳定。经过实际比对验证，比对样品各项特性满足计量比对工作需求，可应用于浊度计的仪器校准、浊度测量结果的质量控制、浊度计量标准的比对和能力验证、期间核查等方面。

关键词：浊度；量值传递；比对；标准样品；不确定度

中图分类号：TQ421.3；TB99  文献标识码：A  文章编号：0258-3283（2021）

Development of Comparison Samples for Turbidity

Gao Xu-hui^*, Huang jin-mei, LI Yu, CHANG Mei, NG Min-zhen (Shaanxi Institute of Metrology，Xi’an 710065, China), Huaxue Shiji, 2021, 43(3)

Abstract: Based on the requirements of international standards, the comparison sample for turbidity was prepared. Its nominal value can be traced back to the national first-class reference material, and the uncertainty U = 3.2% (k =2). The sample has od homogeneity and can keep the value stable within 150 days. After verification by practical comparison, the characteristics of the comparison samples meet the requirements of measurement comparison, and can be used for calibrate the turbid meters, quality control of turbidity measurement results, comparison and capability verification of turbidity measurement standards, and intermediate check.

Key words: turbidity; dissemination of the value of quantity; comparison; reference material; uncertainty

联吡啶羧酸铜配合物的合成及其抑制PTP1B活性研究

李丽¹，高晓丽^*2

（1. 山西工程技术学院 矿业工程系，山西 阳泉  045000；2. 太原师范学院 化学系，山西 晋中  030619）

摘要：以一种柔性紫精衍生物1,1'-双（4-羧苄基）-4,4'-联吡啶二氯化物为配体，合成一种新型联吡啶羧酸铜配合物{[Cu(Bpybc)_1.5(H₂O)₂]·SO₄}_n，对其结构和组成经红外光谱、X-射线单晶衍射和元素分析表征。该配合物属于三方晶系，空间群R-3，晶胞参数为：a = 17.8232(14) ?，b = 17.8232(14) ?，c = 26.987(2) ?，α = 90°，β = 90°，γ = 120°，V = 7424.3(11) ?³，Z = 6，R_int = 0.1347，R₁= 0.0950，T = 293 K。此外，通过体外抑制活性实验研究了该配合物对蛋白酪氨酸磷酸酶1B（PTP1B）的抑制作用，该配合物能够有效抑制PTP1B的活性，其IC₅₀值为0.095 μmol/L。

关键词：蛋白酪氨酸磷酸酶1B（PTP1B）；联吡啶羧酸；铜配合物；抑制作用

中图分类号：O614  文献标识码：A  文章编号：0258-3283（2021）--

Synthesis of {[Cu(Bpybc)_1.5(H₂O)₂]·SO₄}_n Complex and the Inhibition Against Protein Tyrosine Phosphatase 1B

LI Li¹, GAO Xiao-li^*2 (1. Department of Mining Engineering, Shanxi Institute of Technology, Yangquan 045000, China; 2. Department of Chemistry , Taiyuan Normal University, Jinzhong 030619, China), Huaxue Shiji, 2021, 43(3)

Abstract: The insulin-sensitizing effect of metal complexes has been linked to their ability to inhibit protein tyrosine phosphatases1B (PTP1B). Considering that copper complexes may exchange in vivo with aromatic carboxylate ligands, a cooper complex, {[Cu(Bpybc)_1.5(H₂O)₂]·SO₄}_n was synthesized and characterized. The complex crystallizes is in the trinal space group, R-3, a = 17.8232(14) ?, b = 17.8232(14) ?, c = 26.987(2) ?, α = 90°, β = 90°, γ = 120°, V = 7424.3(11) ?³, Z = 6, R_int = 0.1347, R₁ = 0.0950, T = 293 K. The complex showed potent inhibition against PTP1B with IC₅₀ value in the range of 0.095 μmol/L.

Key words: Protein tyrosine phosphatases 1B; Bipyridinium carboxylate; Copper complex; Inhibition

一种高效检测铜离子的罗丹明类荧光探针的构建及应用

贾斌，李漫，郑嘉，郭洁，王铁良，王允，刘冬梅，张迪^*，刘继红

（河南省农业科学院 农业质量标准与检测技术研究所 农业农村部农产品质量安全风险评估实验室(郑州),河南省粮食质量安全与检测重点实验室, 河南 郑州  450002）

摘要：以罗丹明类似物和丹磺酰氯设计并合成了一种“开-关”罗丹明衍生物荧光探针（CuP1），产率较高、产物提纯方法简单，通过核磁氢谱、碳谱和高分辨质谱对其化学结构进行了确证。分析实验结果表明，该探针对铜离子的紫外吸收光谱和荧光发射光谱均表现出专一的选择性和高效的灵敏度，并能够实现裸眼识别；探针对铜离子的识别在铜离子浓度为1～7 μmol/L的范围内呈现良好的线性，最低检出限为1.72 μmol/L，结果满足中国饮用水标准中铜离子含量限量值要求。细胞成像实验结果表明，探针可以应用于生物体系中检测外源性铜离子。探针识别铜离子是不可逆的，其识别机理得到高分辨质谱数据的确证。

关键词：Cu²⁺；荧光探针；罗丹明；细胞成像；检测

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

Construction and Application of Efficient Rhodamine Fluorescent Probe for Cu²⁺ Detection

JIA Bin, LI Man, ZHENG Jia, GUO Jie, WANG Tie-liang, LIU Dong-mei, ZHANG Di^*, LIU Ji-hong (Institute of Agricultural Quality Standards and Testing Technology, Laboratory of Quality & Safety Risk Assessment for Agro-Products (Zhengzhou), Henan Cereal Quality and Safety Testing Key Laboratory, Henan Academy of Agricultural Sciences, Zhengzhou 450002, China), Huaxue Shiji, 2021, 43(3)

Abstract: A kind of "on-off" rhodamine derivative fluorescent probe (CuP1) was designed and synthesized from rhodamine analogues and dansyl chloride. The chemical structure was confirmed by ¹H NMR, ¹³C NMR and HRMS. The probe showed specific selectivity and high sensitivity to both UV absorption and fluorescence spectra of Cu²⁺, and can served as naked-eye detection of Cu²⁺. The linear range of Cu²⁺ concentration is 1～7 μmol/L, and the detection limit of the probe is 1.72 μmol/L, which meets the requirements of the Chinese drinking water standard. The results of cell imaging experiments show that the probe can be used to detect exogenous Cu²⁺ in biological system. The detection of probe with Cu²⁺ is irreversible, and the recognition mechanism of the probe towards Cu²⁺ is confirmed by HRMS data.

Key words: Cu²⁺；fluorescence probe；rhodamine；cell imaging；detection

响应面法优化超声辅助离子液体提取栀子中的西红花苷

李晓严^*，郭蔚，刘鑫玉

（信阳学院 理工学院，河南 信阳  464000）

摘要：以离子液体的醇溶液为溶剂，采用超声辅助的方法提取栀子中的西红花苷，并用高效液相色谱仪测定提取液中西红花苷的含量，由此计算得出提取率。首先选择离子液体种类，再通过单因素实验确定料液比、乙醇体积分数、超声提取时间、离子液体浓度、超声提取温度的最佳参数。以单因素实验结论为基础设计响应面实验，利用Design-Expert 8.0软件对响应面模型进行分析，优化提取工艺的参数。结果表明，以离子液体（[Bmim]BF4）的70%乙醇溶液为提取溶剂，离子液体浓度为0.82 mol/L，超声时间为41.76 min，料液比为1∶20.26（g/mL）时为最佳提取条件，最高提取率可达到1.13%。与普通溶剂相比有很大的优势。

关键词：离子液体；栀子；西红花苷；响应面法；高效液相色谱法

中图分类号：O629.4  文献标志码：A  文章编号：0258-3283(2021)03--

Optimization of Ultrasonic-assisted Ionic Liquid Extraction of Crocin from Gardenia by Response Surface Methodology

LI Xiao-yan^*, GUO Wei, LIU Xin-yu (College of Science and Technology, Xinyang University, Xinyang 464000, China), Huaxue Shiji, 2021, 43(3), ～

Abstract: The alcohol solution of ionic liquid was used as the solvent to extract the crocin from gardenia by ultrasound-assisted method, and the content of crocin in the extract was determined by HPLC, and the extraction rate was calculated. Firstly, the type of ionic liquid was selected, and then the optimal parameters of solid-liquid ratio, ethanol volume fraction, ultrasonic extraction time, ionic liquid concentration, and ultrasonic extraction temperature were determined by single factor experiment. The response surface experiment was designed on the basis of the single-factor experimental conclusion, and the response surface model was analyzed by using the design-expert 8.0 software to optimize the extraction process parameters. The results showed that the best extraction conditions were 70% ethanol solution of ionic liquid ([Bmim]BF₄), the ionic liquid concentration was 0.82 mol/L, the ultrasonic time was 41.76 min, and the ratio of solid to liquid was 1:20.26 g/mL. It has great advantages over common solvents.

Key words: ionic liquid; gardenia; crocin; response surface method; high performance liquid chromatography

SDS-超声辅助提取刺梨果渣黄酮工艺研究

王绪英，赵文，杨洪，廖雯，向红，朱淼^*

(六盘水师范学院 生物科学与技术学院，贵州 六盘水  553000)

摘要：以刺梨果渣为原料，通过SDS-超声辅助的方法，用水和乙醇两种溶剂分别提取总黄酮。在单因素实验基础上，依据Box-Behnken原理优化不同提取方式下刺梨果渣黄酮提取的最优工艺条件。结果表明，以SDS-超声辅助水提取的方法在其最佳工艺参数为料液比1∶47 g/mL，SDS浓度1.26%，超声时间45 min的条件下获得的刺梨果渣黄酮实际得率最高，为0.699%，与预测得率0.711%之间的相对误差为1.72%。而SDS-超声辅助醇提取和未加SDS的醇提取两种方法在各自的最优提取条件下获得的黄酮实际得率分别为0.448%和0.419%。说明SDS-超声辅助水提取的方法更适合刺梨果渣中黄酮的提取，且方法准确可靠。

关键词：刺梨果渣；黄酮；SDS-超声辅助提取；响应面法

中图分类号：R284.2  文献标识码：A  文章编号：0258-3283（2021）

Extraction Technology of Flavonoids from Pomace of Rosa Roxburghii Tratt. by SDS-ultrasound-assisted Methodology

WANG Xu-ying, ZHAO Wen, YANG Hong, LIAO Wen, XIANG Hong, ZHU Miao^* (School of Biological Science and Technology, Liupanshui Normal University, Liupanshui 553000, China), Huaxue Shiji, 2021, 43(3)

Abstract: Total flavonoids from the pomace of Rosa roxburghii Tratt. were extracted by SDS-ultrasound-assisted method with water and ethanol, respectively. Based on single-factor experiments and the Box-Behnken principle, extraction conditions under different extraction methods were optimized. Actual yield of flavonoids was the highest, 0.699%, and the relative error of the predicted yield 0.711% was 1.72%, under the optimum technological parameters of water extraction as follows: Solid-liquid ratio 1:47 g/mL, SDS concentration 1.26%, and ultrasonic time 45 min. However, the actual yields of flavonoids obtained by SDS-ultrasonic-assisted alcohol extraction and SDS-free alcohol extraction under the respective optimal extraction conditions were 0.448% and 0.419%, respectively. SDS-Ultrasound-assisted water extraction was more suitable for extracting flavonoids from Rosa roxburghii Tratt. pomace, and the method was accurate and reliable.

Key words: the pomace of Rosa roxburghii Tratt.; flavonoids; SDS-ultrasonic-assisted extraction; response surface methodology

离子液体法合成氰尿酸绿色新工艺研究

门吉帅¹，王颖，邵长银¹，金志菊¹，李刚^*2，程晋曦

(1. 山东大明消毒科技有限公司，山东 滕州  277599；

2. 西澳大学，化工系，克劳利 西澳州 6009)

摘要：为解决目前氰尿酸工业生产存在的操作困难、环境污染严重等问题，真正实现清洁生产，提出以离子液体为溶媒，通过液相法尿素缩合生成氰尿酸的新型绿色工艺技术，分析其反应机理并对其优化。首先对离子液体进行筛选，研究投料比、投料方式、离子液体回收套用等因素对反应收率和纯度的影响。最终确定较佳条件为，选用1-乙基-3-甲基咪唑四氟硼酸盐做溶媒，尿素和离子液体的投料比为1 ：3（g/mL），缓慢加入尿素并保持反应温度195 ℃，反应时间4 h，离子液体回收率高，回收套用3次后，仍能达到70%以上的收率和90%的纯度。用红外光谱以及核磁共振氢谱确认产物氰尿酸的结构。

关键词：离子液体；1-乙基-3-甲基咪唑四氟硼酸盐；溶媒；尿素；氰尿酸；合成

中图分类号：TQ254  文献标识码：A  文章编号： 0258-3283（2021）

Green Technology of Cyanuric Acid Synthesis by Ionic Liquid

MEN Ji-shuai¹, SHAO Chang-yin¹, JIN Zhi-ju¹, LI Gang^*2 (1. Shandong Daming Disinfection Technology Co. Ltd., Tengzhou 277599, China; 2. Department of Chemical Engineering, University of Western Australia, Crawley 6009, Australia ), Huaxue Shiji, 2021, 43(3)

Abstract：In order to solve the problems existing in the industrial production of cyanuric acid such as operational difficulties and serious environmental pollution, and truly realize clean production, the work proposed a new green process technology that used ionic liquid as a solvent to produce cyanuric acid by the condensation of urea in a liquid phase, analyzed its reaction mechanism and optimized it. The ionic liquids were selected and successively studied the influence of the feeding ratio, feeding method, solvent recovery and other factors on the reaction yield and purity. The appropriate reaction conditions were as follows: Used 1-ethyl-3-methylimidazole tetrafluoroborate as the solvent, the ratio of urea and ionic liquid was 1:3, slowly added urea and kept the reaction temperature at 195 ℃, reaction time 4 h. The recovery rate of ionic liquid was high. After three times of solvent recovery, it can still achieve a yield of more than 70% and a purity of 90%. The structure of product cyanuric acid was confirmed by IR spectrum and ¹HNMR.

Key words: ionic liquid; 1-ethyl-3-methylimidazole tetrafluoroborate; solvent; urea; cyanuric acid; synthesis

一种高效制备硝基乙酸酯的方法

张梅梅¹，杨浩²，谢英花^*1

(1. 河北科技大学 化学与制药工程学院，河北 石家庄  050018；

2. 中山大学 药学院，广东 广州  510006)

摘要：异恶唑为母核的化合物具有多种生物活性，如抗癌、抗菌、抗病毒、抗炎、镇痛等。硝基乙酸酯是制备异恶唑类化合物重要的原料，报道了一种新型的硝基乙酸酯类化合物的通用合成方法，共合成4个硝基乙酸酯类化合物。其中以3-羟基丙腈和2,2,6-三甲基-1,3-二氧(杂)芑-酮为原料，经亲核取代、缩合、氧化，3步反应得到硝基乙酸-3-丙腈酯，其结构经IR、¹HNMR、¹³CNMR和HR-MS表征，总产率为71.6%。新的合成方法具有操作简单、成本低廉、反应条件温和等优点，适合工业化生产。

关键词：硝基乙酸酯；异恶唑；杂环化合物；医药中间体；合成

中图分类号：O623.71  文献标识码：A  文章编号：0258-3283（2021）

An Efficient Method for Preparation of Nitroacetate

ZHANG Mei-mei¹, YANG Hao², XIE Ying-hua^*1 (1. School of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China; 2. School of Pharmaceutical Sciences, Sun Yat-Sen University, Guangzhou 510006, China), Huaxue Shiji, 2021, 43(3)

Abstract: Isoxazoles as the parent nucleus have a variety of biological activities, such as anti-cancer, antibacterial, antiviral, anti-inflammatory, analgesic, and so on. Nitroacetate is an important raw material for the preparation of isoxazole compounds. A novel general synthetic method of nitroacetate was reported, four nitroacetate compounds were synthesized. 2-Cyanoethyl 2-nitroacetate was synthesized from 3-hydroxypropionitrile and 2,2,6-trimethyl-4H-1,3-dioxin-4-one via nucleophilic substitution, condensation and oxidation. The structure was characterized by IR, ¹HNMR, ¹³CNMR and HR-MS in the overall yield of 71.6%. The novel synthetic method has the advantages of simple operation, low costs, and mild reaction conditions, which is suitable for industrial production.

Key words: nitroacetate; isoxazoles; heterocyclic compounds; medical intermediate; synthesis

6-卤代咪唑并[1,2-a]吡啶-3-甲酰胺的简便合成研究

程伟¹，张向龙²，袁文鹏^*1

（1. 齐鲁工业大学（山东省科学院） 山东省科学院菏泽分院 山东省生物工程技术创新中心，山东 菏泽274000；2. 山东友帮生化科技有限公司 山东省小分子杂环化合物工程实验室，山东 菏泽  274000）

摘要：标题化合物是重要的药物中间体，广泛应用于抗癌药物、抗病毒药物的生产。以2-氨基-5-卤代吡啶为起始原料,与N,N-二甲基甲酰胺二甲基缩醛制备亚胺化合物，再和溴乙酸甲酯成环缩合制备6-卤代咪唑并[1,2-a]吡啶-3-甲酯，然后直接与氨气发生氨解反应，共3步反应合成标题化合物，总产率为73.8%～82.5%。产物结构经¹H NMR、¹³C NMR、元素分析进行了表征。与已有的文献方法相比较，此合成路线具有合成方法新颖、操作简单、反应时间短、产率高、避免柱层析分离纯化、更适合工业化放大生产的特点。

关键词：2-氨基-5-卤代吡啶；氨气；6-卤代咪唑并[1,2-a]吡啶-3-甲酰胺；合成；药物中间体；抗癌药物

中图分类号：R914.5  文献标识码：A  文章编号：0258-3283（2021）

Synthesis of 6-Haloimidazo[1,2-a]pyridines-3-carboxamide

CHENG Wei¹, ZHANG Xiang-long², YUAN Wen-peng^*1 (1. Biological Engineering Technology Innovation Center of Shandong Province, Heze Branch, Qilu University of Technology (Shandong Academy of Sciences), Heze 274000, China; 2. Shandong Engineering Laboratory of Small Molecule Heterocyclic Compounds, Shandong Youbang Biochemical Technology Co., Ltd., Heze 274000, China), Huaxue Shiji, 2021, 43(3)

Abstract： The title compounds are important intermediates of drugs, which can be widely used in the production of anti-cancer drugs and anti-virus drugs. In order to optimize the synthetic route, taking 2-amino-5-halopyridine as the raw materials, the synthesis gradually went through the following three-step reaction processes with the total yield of 73.8%～82.5%: reaction with N,N-dimethylformamide dimethyl acetyl to aford N'-(5-halo-2-pyridinyl)-N,N-dimethylimidoformamide, ring-closing condensation with methyl bromoacetate to aford 6-haloimidazo[1,2-a]pyridine-3-carboxylic acid methyl ester, ammonolysis reaction with ammonia to aford 6-haloimidazo [1,2-a] pyridines-3-carboxamide. The structures were confirmed by ¹H NMR, ¹³CNMR and elemental analysis. Compared with the reported synthetic routes, the protocol takes the advantages of new synthetic route, easy operation, and high yield, avoiding column chromatography separation and suited for scale-up production.

Key words: 2-amino-5-halopyridine; ammonia; 6-haloimidazo [1,2-a] pyridines-3-carboxamide; synthesis; drug intermediate; anti-cancer drugs