【综述与专论】
三氟甲基化试剂的研究进展
牛腾*1，杨天宇2，邓周斌3, 姜立萍1，魏惠荣1，刘琦敏1，张慧芳1，郭昊岩1
(1. 兰州文理学院 化学化工学院，甘肃 兰州 730000；2. 北京大学 化学与分子工程学院，北京 100871；3. 西北师范大学 化学化工学院，甘肃 兰州 730070)
摘要：近年来，三氟甲基化成为有机氟化学的研究热点，其主动驱动力是含有三氟甲基基团的有机分子常常表现出独特的物理和化学性质，具有广泛的应用。三氟甲基试剂是向目标分子中引入三氟甲基基团的重要方法之一。综述了三氟甲基化试剂的类型、特点、适用范围等，并对三氟甲基试剂的应用前景作出了展望。
关键词：三氟甲基化；三氟甲基试剂；亲核三氟甲基化试剂；亲电三氟甲基化试剂；自由基三氟甲基试剂
中图分类号：O621.3 文献标识码：A 文章编号：
Research Progress in Trifluoromethylation Reagents NIU Teng*1, YANG Tian-yu2, DENG Zhou-bin3, JIANG Li-ping1, WEI Hui-rong1, LIU Qi-min1, ZHANG Hui-fang1, GUO Hao-yan1 (1. School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou 730000, China; 2. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 3. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China)
Abstract: Organic molecules containing trifluoromethyl groups often exhibit unique physical and chemical properties, and have found extensive applications. Therefore, they have become a hot research topic in organic fluorochemistry. Among these methods, trifluoromethylation is a critical method to install trifluoromethyl group into organic molecules. Their characteristics, scope, limitations, as well as reactive mechanism were discussed in detail, and a perspective on the further development by using trifluoromethylation reagents was put forward.
Key words: trifluoromethylation; trifluoromethylation reagents; electrophilic trifluoromethylation reagents; nucleophilic trifluoromethylation reagents; radical trifluoromethylation reagents
引用本文：牛腾，杨天宇，邓周斌，等. 三氟甲基化试剂的研究进展[J]. 化学试剂，2022，44(12): 1695-1704。
指纹氨基酸检测技术及其在法庭科学中的应用
田师思1a，王利雪2，李泽龙1b，刘兆伦1a，刘硕1a，张婧文1a，赵雅彬1a*
(1. 中国人民公安大学 a.侦查学院，b. 信息网络安全学院，北京 100038；
(2. 安徽省公安教育研究院，安徽 合肥 230031)
摘要：指纹是犯罪现场最重要的痕迹物证之一。氨基酸是指纹内源性分泌物的主要成分，指纹遗留物中的氨基酸常用作显现指纹纹线的反应物。但现场指纹往往模糊而缺乏形态学价值，检测潜在指纹中氨基酸含量并挖掘其更多维的证据信息则成为法庭科学领域的必然趋势。化学分析方法和生物学分析方法使得检测指纹中的超微量氨基酸成为可能。从氨基酸及其检测方法与在法庭科学中的应用展开综述，并比较各种化学分析方法的优劣，以期为氨基酸检测技术在法庭科学的应用奠定理论基础。
关键词：指纹；氨基酸；超微量检测；法庭科学；串联质谱
中图分类号：O657.34 文献标识码：A 文章编号：0258-3283（2022）--
Detection Technologies of Amino Acids in Fingerprint and Their Applications in Forensic Science TIAN Shi-si1a, WANG Li-xue2, LI Ze-long1b, LIU Zhao-lun1a, LIU Shuo1a, ZHANG Jing-wen1a, ZHAO Ya-bin1a* (1. a. Academy of Investigate and Forensic Science, b. Academy of Police Information Engineering and Network Security, People＇s Public Security University of China, Beijing 100032, China; 2.Anhui Public Security Education Research Institute, Hefei 230031, China)
Abstract: Fingerprints are one of the most important trace evidences at crime scenes. Amino acids are the main components of endogenous secretions of fingerprints, and amino acids in fingerprint residues are often used as target reactants for showing fingerprint ridge. However, fingerprints at crime scenes are often ambiguous and lack morphological value. It has become an inevitable trend in forensic science to detect amino acid content in potential fingerprints and excavate its more multidimensional evidence information. Chemical analysis methods and biological analysis methods make it possible to detect ultra-micro amino acids in fingerprints. This paper reviews amino acids and related detection methods and their applications in forensic science. The advantages and disadvantages of various chemical analysis methods are compared in order to lay a theoretical foundation for the application of amino acids detection technologies in forensic science.
Key words：fingerprint ;amino acid；ultra-micro detection；forensic science；tandem mass spectrometry
引用本文：田师思，王利雪，李泽龙，等. 指纹氨基酸检测技术及其在法庭科学中的应用[J]. 化学试剂，2022，44(12): 1705-1711。
不对称催化制备手性苯并磺内酰胺的研究进展
李延顺1，曹国锐1，郭伟2，孟春甫1，滕大为*1
(1. 青岛科技大学，化工学院，山东 青岛 266042；2. 山东达因海洋生物制药股份有限公司，山东 威海 264300)
摘要：手性苯并磺内酰胺类化合物广泛存在于各种药物结构和天然产物中，是抗菌、抗肿瘤、抗病毒等药物的重要组成部分。有机小分子催化剂和有机金属配合物催化剂的发展，使催化不对称合成手性苯并磺内酰胺领域涌现大量研究成果。综述了手性苯并磺内酰胺的不对称催化合成方法进展，包括不对称氢化还原、有机硼试剂不对称加成、不对称傅克反应和不对称曼尼希反应等反应类型，并重点阐述了不同类型的手性催化剂或手性配体对反应产率和对映选择性的影响。
关键词：手性苯并磺内酰胺；不对称合成；手性催化剂；产率；对映选择性
中图分类号：O625.29 文献标识码：A 文章编号：0258-3283（2022）--
Research Advances on Asymmetric Catalyzed Synthesis of Chiral Benzosultams LI Yan-shun1, CAO Guo-rui1, GUO Wei2, MENG Chun-fu, TENG Da-wei*1 (1. College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China; 2. Shandong DYNE Marine Biopharmaceutical Co., Ltd., Weihai 264300, China)
Abstract：Chiral benzosultams are widespread among various drug structures and natural products, and play as an important component in antibacterial drugs, antineoplastic drugs, antiviral drugs, etc. A large number of scientific research results have emerged in the field of asymmetric synthesis with the development of organocatalysts and organometallic complexes. The research advances of asymmetric catalytic synthesis reactions of chiral benzosultams, including asymmetric hydrogenation reaction was reviewed, organoboron reagent asymmetric addition reaction, asymmetric Friedel-Crafts reaction and asymmetric Mannich reaction, and highlights the effect of chiral catalyst or chiral ligand on reaction yield and enantioselectivity.
Key words：chiral benzosultams; asymmetric synthesis; chiral catalyst; yield; enantioselectivity
引用本文：李延顺，曹国锐，郭伟，等. 不对称催化制备手性苯并磺内酰胺的研究进展[J]. 化学试剂，2022，44(12): 1712-1722。
【生化与药用试剂】
低共熔溶剂在生物催化中的应用研究进展
仝争，王渝，何晓希，赵祥杰，王朝宇，杨荣玲*，谢烨晴
（淮阴工学院 生命科学与食品工程学院，江苏 淮安 223003）
摘要：近年来，新型低共熔溶剂（Deep eutectic solvents，DESs）不断开发，已成为替代传统有机溶剂和离子液体的一种绿色溶剂，其具有熔点低、不易挥发、易合成、成本低、易回收等优点，在生物催化反应中具有重要的应用前景。对不同DESs的结构及类型进行了总结，并对其密度、粘度、导电性、凝固点、热稳定性等理化性质进行了详细说明，进而对其细胞毒性和生物降解性进行了阐述，重点对其在酯交换反应、还原反应、水解反应等生物催化反应中的应用进行了总结，进一步对存在的问题和研究的方向进行了总结和展望。
关键词：低共熔溶剂；性质；生物催化；细胞毒性；生物降解性
中图分类号：TQ413 文献编识码：A 文章编号：
Research Progress on the Properties of Deep Eutectic Solvents and Their Application in Biocatalysis TONG Zheng, WANG Yu, HE Xiao-xi, ZHAO Xiang-jie, WANG Zhao-yu, YANG Rong-ling*, XIE Ye-qing (Huaiyin Institute of Technology, School of Life Science and Food Technology, Huai’an 223003, China)
Abstract: New deep eutectic solvents (DESs) have been continuously developed in recent years, which have been shown to be a kind of green solvents that could replace traditional organic solvents and ionic liquids in biological catalysis reactions. DESs have displayed the advantages of low melting point, non-volatile, easy synthesis, low cost and easy recovery properties. They have important application prospects in biocatalytic reactions. The structure and types of different DESs summarized and its physical and chemical properties such as density, viscosity, conductivity, freezing point and thermal stability are described in detail. And, the cytotoxicity and biodegradability characteristics of DESs are also introduced, with emphasis on its application in biocatalytic reactions such as esterification reaction, reduction reaction and hydrolysis reaction. Further, the existing problems and research directions are summarized and prospected.
Key words: deep eutectic solvent; properties; biocatalysis; cytotoxicity; biodegradability
引用本文：仝争，王渝，何晓希，等. 低共熔溶剂在生物催化中的应用研究进展[J]. 化学试剂，2022，44(12): 1723-1730。
二硫代氨基甲酸盐金配合物的抗肿瘤活性研究进展
陈秋梅，陈施施，吴相华*
（云南师范大学 化学化工学院，云南 昆明 650500）
摘要：金属配合物作为抗癌药物的研究已受到广泛关注。金属药物的毒性、生物利用度和特异性可由金属配合物的结构和配体属性进行微调。金（Ⅰ，Ⅲ）配合物因具有优良的抗肿瘤活性被广泛研究。拥有配位功能的二硫代氨基甲酸盐具有潜在的化学保护功能，可治疗细菌和真菌感染，以及癌症。稳定的二硫代氨基甲酸盐配体与金（Ⅰ，Ⅲ）的结合物因展现出优异的抗肿瘤活性而被广泛关注和研究，为癌症治疗提供了一种新的有效方法。主要综述了二硫代氨基甲酸盐金（Ⅰ）和金（Ⅲ）配生物的抗肿瘤活性研究进展，以期为相关研究和应用提供参考。
关键词：金属药物；二硫代氨基甲酸盐；金（Ⅰ，Ⅲ）配合物；抗肿瘤；作用机制
中图分类号：R914.3 文献标识码：A 文章编号：0258-3283（2022）--
Progress in Antitumor Activity of Dithiocarbamate Gold Complexes CHEN Qiu-mei, CHEN Shi-shi, WU Xiang-hua* (College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China)
Abstract：The research of metal complexes as anticancer drugs has attracted extensive attention. The toxicity, bioavailability, and specificity of metallodrug candidates can be fine-tuned by the structure of metal complexes and the properties of ligand. Gold (Ⅰ, Ⅲ) complexes have been widely studied because of their excellent antitumor activity. Coordinated dithiocarbamates are reported to possess potential chemoprotective function, treatment of bacterial and fungal infections, and cancer. The combination of stable dithiocarbamate ligand and gold (Ⅰ, Ⅲ) has been widely concerned and studied because of its excellent antitumor activity, which provides a novel and effective method on cancer treatment. The research progress of antitumor activity of dithiocarbamate gold(Ⅰ) and gold(Ⅲ) complexes was reviewed, which aims to provide reference for related research and application.
Keywords：metallodrugs; dithiocarbamates; gold(Ⅰ, Ⅲ) complex; antitumor; mechanism of action
引用本文：陈秋梅, 陈施施, 吴相华. 二硫代氨基甲酸盐金配合物的抗肿瘤活性研究进展[J]. 化学试剂, 2022, 44(12):1731-1737.
【功能材料】
纤维素/丝素蛋白复合水凝胶作为金纳米粒子的选择性载体：合成和催化应用研究
薛新新，邹光龙*
(贵州民族大学 化学工程学院，贵州 贵阳 550025)
摘要：展示了一种以乙酰丙酸基质子型离子液体（Lev-PILs）为溶剂制备纤维素/丝素蛋白复合水凝胶（CSH）的新工艺。并利用水凝胶在负载贵金属纳米粒子上的优势，实现了在CSH中原位负载Au纳米粒子，最终得到三种不同比例的CSH@Au复合材料。通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能量色散X射线光谱（EDX）、X射线衍射（XRD）和电感耦合等离子体发射光谱（ICP-OES）等一系列手段对复合材料的性质进行了研究，结果表明CSH对金纳米粒子具有良好的固定能力和选择性吸附能力。将制备的CSH@Au复合材料用来催化水中污染物—对硝基苯酚（4-Np）的还原反应。结果显示，CSH@Au复合材料具有优异的催化性能和循环使用性能。此外，对该反应的动力学进行了深入的研究，最终活化参数通过计算可得Ea=20.71 kJ/mol，ΔH#=17.84 kJ/mol和ΔS#=−268.0 J/(mol·K)。丝素蛋白在水凝胶中的存在被证明是稳定金纳米颗粒的关键因素，这是由于金属和载体之间的相互作用，利用这种方法可以扩展到制备其他不同用途的纳米颗粒。
关键词：纤维素；丝素蛋白；水凝胶；金纳米粒子；催化过程；4-硝基苯酚
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2022）--
Cellulose/silk fibroin composite hydrogels as selective support carriers of gold nanoparticles: synthesis and catalytic application research XUE Xin-xin, ZOU Guang-long* (School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China)
Abstract：A new process for the preparation of cellulose/silk fibroin composite hydrogels (CSH) using levulinate-based protic ionic liquids (Lev PILs) as solvent was demonstrated. Taking advantage of hydrogel in loading noble metal nanoparticles, three different ratios of CSH@Au composites were obtained by in-situ loading of Au nanoparticles in CSH. The properties of the composites were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and inductively coupled plasma-atomic emission spectroscopy (ICP-OES). The results showed that CSH had good immobilization and selective adsorption ability for gold nanoparticles. The prepared CSH@Au composites were used to catalyze the reduction reaction of 4-nitrophenol (4-NP), a pollutant in water. Moreover, the prepared composites had excellent catalytic performance and recycling performance. And the kinetics of the reaction were studied in depth, where the activation parameters were calculated to be Ea = 20.71 kJ/mol, ΔH# = 17.84 kJ/mol, and ΔS# = −268.0 J/(mol·K). The presence of silk fibroin in the hydrogel had been proved to be a key factor in stabilizing gold nanoparticles due to the interaction between the metal and the carrier. This method can be extended to the preparation of nanoparticles for other different purposes.
Key words：cellulose; silk fibroin; hydrogel; Au nanoparticles; catalytic process; 4-nitrophenol
引用本文：薛新新，邹光龙. 纤维素/丝素蛋白复合水凝胶作为金纳米粒子的选择性载体：合成和催化应用研究[J]. 化学试剂，2022，44(12):1738-1746。
碳热还原一步构建氧化铝修饰CuNi合金催化剂及其乙酰丙酸转移加氢性能
俞南汐a，鲁厚芳b，吴可荆*a
(四川大学 a.新能源与低碳技术研究院，b.化工工程学院，四川 成都 610065)
摘要：在以异丙醇为氢供体的乙酰丙酸转移加氢反应中，催化剂需同时具有用于氢转移的加氢位点和用于乙酰丙酸与醇酯化的酸性位点。以氧化铝为酸性位点，铜镍为加氢位点，以碳热还原法一步构建了酸修饰的CuNi合金催化剂。碳热还原温度大于450 ℃时，能得到CuNi合金；过高的还原温度下，部分铜还没有进入合金相就已经被还原成Cu2O，不利于铜镍合金的形成。还原温度较低的催化剂上虽然零价金属较少，但反应过程中异丙醇能把金属氧化物还原至零价金属；还原温度较高时，得到的零价金属较多，但颗粒团聚更严重。这些作用拉平了还原温度的影响，在300～600 ℃下碳热还原得到的催化剂表现出相近的催化活性。
关键词：转移加氢；乙酰丙酸；酸性位；CuNi合金；碳热还原
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2022）--
Alumina-modified CuNi Alloy Catalyst Prepared by One-step Carbothermic Reduction and Its Levulinic Acid Transfer Hydrogenation Properties YU Nan-xia, LU Hou-fangb, WU Ke-jing*a (1. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China; 2. School of Chemical Engineering, Sichuan University, Chengdu 610065, China)
Abstract：In the transfer hydrogenation reaction of levulinic acid with isopropanol as hydrogen donor, the catalyst should have both a metal site for hydrogen transfer and an acid site for the esterification of levulinic acid with alcohol. In this paper, acid modified CuNi alloy catalyst was constructed by carbothermic reduction with alumina as acid site and copper and nickel as hydrogenation site. CuNi alloy can be obtained when the reduction temperature is higher than 450 ℃. At high reduction temperature, part of copper has been reduced to Cu2O before entering the alloy phase, which is not conducive to the formation of CuNi alloy. Catalysts with lower reduction temperatures have less zero-valent metals, but isopropanol can reduce metal oxides to metals in the reaction. When the calcination temperature is higher, more zero-valent metals are obtained, but the agglomeration of particles is more serious. These effects smoothen the effect of reduction temperature, and the catalyst obtained by carbothermic reduction at 300～600 ℃ exhibits similar catalytic activity.
Key words：transfer hydrogenation; levulinic acid; acid site; CuNi alloy; carbothermal reduction
引用本文：俞南汐，鲁厚芳，吴可荆. 碳热还原一步构建氧化铝修饰CuNi合金催化剂及其乙酰丙酸转移加氢性能[J]. 化学试剂,2022,44(12): 1747-1755。
高强度稀土纳米复合发光水凝胶中的级联能量传递
朱孔义1，董宁宁2，秦艳1，李彬2，李志强*2
(1. 内蒙古伊泰石化有限责任公司，内蒙古 鄂尔多斯 010700；2. 河北工业大学 化工学院，天津 300130)
摘要：光捕获系统在自然光合作用和光电子器件中发挥着重要作用。制备具有多步连续能量转移特征，并能实现高效能量传递的光捕获材料对解决人类面临的能源问题和人工模拟光合作用都具有重要意义。水凝胶与生物体中的许多组织，如肌肉、软骨和皮肤等具有相似的结构，加之其良好的生物相容性，使得它比其他任何人工材料更接近于活体组织，是人造替代器官的理想材料。因此，水凝胶中的光捕获系统更加备受关注。通过将稀土配合物、N-异丙基丙烯酰胺（NIPA）、罗丹明B（RhB）和锂皂石纳米片原位共聚合构筑了高强度纳米复合发光水凝胶。该水凝胶实现了从天线分子到稀土再到RhB的级联能量传递。与目前被广泛报道的超分子凝胶能量传递体系相比，锂皂石和稀土配合物同时作为交联剂显著提高了水凝胶的机械强度，该策略有望为高强度光捕获凝胶体系的构筑提供一种通用方法。
关键词：稀土配合物；水凝胶；能量传递；锂皂石；荧光性能
中图分类号：O64 文献标识码：A 文章编号：0258-3283（2022）
Sequential Energy Transfer in Tough Nanocomposite Luminescent Hydrogel ZHU Kong-yi1, DONG Ning-ning2, QIN Yan1, LI Bin2, LI Zhi-qiang*2 (1. Inner Mongolia Yitai Petrochemical Co. LTD, Erdos 010700, China; 2. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China)
Abstract：Light harvesting system plays an important role in photosynthesis and photoelectronic devices, thus, the preparation of light capture materials with efficient sequential energy transfer characteristics is of great significance for solving energy problems and artificial simulating photosynthesis. Hydrogels have similar structures to many tissues, such as muscle, cartilage, and skin, together with good biocompatibility, making them promising candidates for artificial organs. Therefore, light harvesting in hydrogels has attracted more attention. We reported the construction of nanocomposite luminescent hydrogel via in situ copolymerization of lanthanide complex, NIPA, Rhodamine B, and laponite nanosheets. Sequential energy transfer from antenna molecule to lanthanide ion, and Rhodamine B was observed. Both laponite nanosheets and lanthanide complex can crosslink the hydrogel network and thus significantly improve the mechanical strength of the obtained nanocomposite hydrogels. This strategy is expected to provide a general method for the construction of a light harvest system in the robust hydrogel.
Key words：lanthanide complex; hydrogel; energy transfer; laponite; luminescence
引用本文：朱孔义，董宁宁，秦艳，等. 高强度稀土纳米复合发光水凝胶中的级联能量传递[J] 化学试剂，2022，44(12)：1756-1761.
吲哚乙酸磁性分子印迹聚合物的制备及性能研究
刘恋，冯淋，乔晨，樊世萌，尤祥宇*，苏江涛
（湖北工业大学 生物工程与食品学院，湖北 武汉 430068）
摘要：以氨基化磁性材料为内核，以吲哚乙酸（IAA）为模板分子、甲基丙烯酸（MAA）为功能单体、偶氮二异丁腈（AIBN）为引发剂、乙二醇二甲基丙烯酸酯（EGDMA）为交联剂、乙腈为溶剂制备核壳型磁性分子印迹聚合物（IAA-MMIPs）。探索了模板、功能单体和交联剂的最佳比例及最优聚合时间；通过等温吸附、动力学吸附及人工尿样中对IAA的吸附等实验，对IAA-MMIPs的吸附性能进行评价。结果显示，IAA-MMIPs对IAA有较强的吸附效果，在人工尿样中对IAA的吸附能力显示出较好的应用潜力。
关键词：吲哚乙酸；尿毒症毒素分子；分子印迹；吸附
中图分类号：TB34 文献标识码：A 文章编号：0258-3283（2022）
Preparation and Properties of Magnetic Molecularly Imprinted Polymer of Indole Acetic Acid LIU Lian, FENG Lin, QIAO Chen, FAN Shi-meng, YOU Xiang-yu*, SU Jiang-tao (School of Bioengineering and Food science, Hubei University of Technology, Wuhan 430068, China)
Abstract：The design and preparation of adsorbent materials for protein-bound uremic toxins, such as indoleacetic acid (IAA), is of interest in the field of hemodialysis. Core-shell magnetic molecularly imprinted polymers (IAA-MMIPs) were prepared with aminoated magnetic materials as cores, IAA as template molecule, methacrylic acid (MAA) as functional monomer, 2,2'-azodiisobutyronitrile (AIBN) as initiator, ethylene glycol dimethacrylate (EGDMA) as cross-linker, and acetonitrile as solvent. The optimal ratio of template, functional monomer, and cross-linker and the optimal polymerization time were explored. The adsorption performance of IAA-MMIPs was evaluated by isothermal adsorption, kinetic adsorption, and adsorption of IAA in artificial urine samples. The results showed that IAA-MMIPs had a strong adsorption effect on IAA. The adsorption ability of IAA-MMIPs on IAA in artificial urine samples demonstrated its potential for application in complex sample environments such as hemodialysis.
Key words: indoleacetic acid; uremic toxins; molecular imprinting; adsorption
引用本文：刘恋, 冯淋, 乔晨, 等. 吲哚乙酸磁性分子印迹聚合物的制备及性能研究[J]. 化学试剂, 2022,44（12）：1762-1767 .
【分离提取技术】
菱角壳木质素提取分离及其抗氧化活性评价
李锋a,b，毛海立a,b，曾承露a，徐平*a
（黔南民族师范学院 a. 化学化工学院，b. 黔南环境治理与污染控制工程研究中心，贵州 都匀 558000）
摘要：为研究菱角壳木质素的结构和功能特性，采用4种方法提取分离菱角壳中木质素，利用紫外吸收光谱、凝胶渗透色谱、傅里叶变换红外光谱和热重分析进行木质素结构表征，并对其抗氧化活性进行评价。结果表明：4种方法提取的菱角壳木质素结构保留完整，主要有紫丁香基和愈创木酚基结构单元组成。除碱木质素外，其他木质素的相对分子量较低，且分散度均小于2.5。热重分析表明菱角壳木质素热解过程主要发生在200 ～ 500 ℃之间。此外，4种木质素均表现出良好的抗氧化活性，其中在木质素浓度为0.4 mg/mL时，AAL、p-TsOH和Bet/LA对DPPH自由基清除率分别可达84.63%、86.62%和62.3%。通过本研究以期为菱角壳组分分离和高值化开发利用提供技术支撑。
关键词：菱角壳；木质素；结构表征；抗氧化活性；热解
中图分类号：TQ35 文献标识码：A 文章编号：0258-3283（2022）
Evaluation of Antioxidant Activity of Lignin Extracted from Water Caltrop Shell LI Fenga,b, MAO Hai-lia,b, ZENG cheng-lu a, XU ping*a (a. School of Chemistry and Chemical Engineering, b. Qiannan Engingineering Research Center for Environmental Governanen and Contamination Control, Qiannan Normal College for Nationalities, Duyun 558000, China)
Abstract: Four lignin samples were isolated and their structural characteristic were investigated using ultraviolet spectroscopy (UV), infrared spectroscopy (FTIR), gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The evaluation of the antioxidant activity showed that the benzene ring of lignin with syringl and guaiacyl units remained complete. Compared to AL, the other lignin samples presented low relative molecular mass and polydispersity index (PDI < 2.5). TGA showed that the thermal stability of lignin samples was excellent, and most of them degraded in the temperature range of 200～500 ℃. Moreover, these four samples exhibited distinct antioxidant activity. Under the lignin concentration of 0.4 mg/mL, the capability of AAL, p-TsOH, and Bet/LA samples to scavenge DPPH radical were up to 84.63%, 86.62% and 62.3%, respectively. These findings provide a novel way to fractionate lignin from water caltrop shell, contributing to extend the opportunities of lignin valorization into added-value products.
Key words: water caltrop shell; lignin; structural characterization; antioxidant; pyrolysis
引用本文：李锋,毛海立,曾承露,等. 菱角壳木质素提取分离及其抗氧化活性评价[J]. 化学试剂，2022, 44(12):1768-1774.
基于苄基三乙基溴化铵和正辛酸的低共熔溶剂的制备及其在分散液液微萃取中的应用
葛丹丹*1，黄兴2，马兴娅1，石毓秀1
(1. 昆明学院 化学化工学院，云南 昆明 650214；2. 中国热带农业科学院环境与植物保护研究所，海南 海口 571101)
摘要：以苄基三乙基溴化铵和正辛酸制备出新型低共熔溶剂，并作为萃取溶剂建立了漩涡辅助分散液-液微萃取结合高效液相色谱测定3种苏丹红染料的方法。对影响萃取效率的各种参数，包括低共熔溶剂的组成、萃取时间、萃取剂用量、溶液pH值和盐浓度等进行了优化。结果表明最佳萃取条件为：以苄基三乙基溴化铵物质的量比1∶2制备出的低共熔溶剂为萃取溶剂，萃取剂用量为50 µL，萃漩涡时间为2 min，溶液pH 7，盐浓度为0 mg/mL。在最优化条件下，3种苏丹红染料在8～1000 ng/mL范围内线性关系良好，相关系数均大于0.9956，检出限和定量限范围分别为2～2.5 ng/mL和6～8 ng/mL，对果汁和环境水样进行加标实验，回收率为82.3%～111.5%，相对平均偏差范围为0.5%～7.2%。该方法简单、快速、绿色环保，可用于真实样品中苏丹红染料的分析检测。
关键词：低共熔溶剂；分散液-液微萃取；苏丹红染料；饮料分析；水样分析
中图分类号：O661.1 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of a deep eutectic solvent based on benzyltriethylammonium bromide and octanoic acid and its application in dispersion liquid-liquid microextractionGE Dan-dan*1, HUANG Xing2, MA Xing-ya1, SHI Yu-xiu1 (1. School of Chemistry and Chemical Engineering, Kunming University, Kunming 650214, China; 2. Environment and Plant Protection Institute, Chinese Academy of Tropical Agricultural Sciences, Haikou 571101, China)
Abstract: A new hydrophobic deep eutectic solvent (DES), formed from benzyltriethylammonium bromide and octanoic acid, was used as an extraction solvent in vortex-assisted dispersive liquid-liquid microextraction combined with high-performance liquid chromatography for the preconcentration and detection of three Sudan dyes from food samples. Factors affecting the extraction efficiency including the type and volume of extraction solvent, extraction time, solution pH and salt concentration were optimized. The optimum extraction conditions were: volume of extraction solvent was 50 μL, vortex time was 2 min, solution pH was 7, salt concentration was 0 mg/mL. Under the optimized condition, a linear range was in the range of 10～1000 ng/mL with a correlation coefficient higher than 0.9956, limits of detection ranged from 2 to 2.5 ng/mL, and limits of quantification from 6 to 8 ng/mL. The food samples were spiked with 20, 50, and 100 ng/mL of Sudan dyes, and the extraction recoveries ranged from 82.3% to 111.5% with RSDs ranging from 0.5% to 7.2%. The developed method is simple, quick, and environmentally friendly, which can be applied to detect the Sudan dyes in real food samples.
Keywords: deep eutectic solvent; dispersive liquid-liquid microextraction; Sudan dyes; food analysis; environmental water analysis
引用本文：葛丹丹，黄兴，马兴娅，等. 基于苄基三乙基溴化铵和正辛酸的低共熔溶剂的制备及其在分散液液微萃取中的应用[J]. 化学试剂,2022, 44(12): 1775-1781。
电子级3-乙氧基丙酸乙酯的提纯制备
杨长青*1，邹德强2，王大松1，马群1
（1. 北京化学试剂研究所有限责任公司，北京 大兴 102607；2. 大连第一有机化工有限公司，辽宁 大连 116308 ）
摘要：电子级3-乙氧基丙酸乙酯（EEP）是集成电路（IC）和液晶面板（LCD）行业必须的清洗剂和溶剂。着重研究适合大规模生产的电子级EEP的提纯工艺，实验采用工业级EEP为原料，使用吸附、离子交换、反应精馏等工艺进行提纯，产品满足电子级3-乙氧基丙酸乙酯SEMI G3指标要求。分析3-乙氧基丙酸乙酯的分解原因和精馏液泛的原因，通过改变交换基来减少EEP的分解，通过计算对液泛速度和塔径进行修正，解决液泛问题。
关键词：电子级3-乙氧基丙酸乙酯（EEP）；提纯；分子筛；离子交换；精馏；液泛
中图分类号：TQ 421.4 文献标识码：A 文章编号：0258-3283（2022）
The Purification of Electronic Grade Ethyl 3-ethoxypropionate YANG Chang-qing*1, ZOU De-qiang2, WANG Da-song1, MA Qun1 (1. Beijing Institute of Chemical Reagents Co., Ltd., Beijing 102607, China; 2. Dalian First Organic Chemical Co.,Ltd., Liaoning 116308, China)
Abstract: Electronic grade ethyl 3-ethoxypropionate (EEP) is a necessary cleaning agent and solvent in the integrated circuit (IC) and liquid crystal display (LCD) industry. The purification process of electronic grade EEP suitable for large-scale industrial production was studied. Industrial EEP was used as the raw material in the experiment. Many processes including adsorption, ion exchange, and reactive distillation were applied in the purification, and the resulted product met the requirements of SEMI G3 for Electronic grade EEP. The reasons for the decomposition of ethyl 3-ethoxypropionate and the flooding of distillation were analyzed. The decomposition of EEP was reduced by changing the exchange basis. The problem of distillation flooding was solved by calculation to correct the flooding speed and tower diameter.
Key words: electronic grade ethyl 3-ethoxypropionate (EEP); purification; molecular sieve; ion exchange; reactive distillation; flooding.
引用本文：杨长青，邹德强，王大松，等. 电子级3-乙氧基丙酸乙酯的提纯制备[J]. 化学试剂，2022，44（12）：1782-1788。
【电化学和新能源】
甘氨酸辅助浸渍法制备高分散Ni/SBA-15低温甲烷干重整催化剂研究
杨继亮a,b，鲁新康a, b，韩翠a, b，刘辉c，公丹丹a, b，王路辉*a, b
（ 浙江海洋大学 a.浙江省石油化工环境污染控制重点实验室,
b.石油化工与环境学院,c.食品与药学学院，浙江 舟山 316022）
摘要：甲烷干重整反应可以将甲烷和二氧化碳这两种温室气体转化为更有价值的合成气，而镍基催化剂被认为是最有应用前景的甲烷干重整催化剂之一。将Ni/SBA-15催化剂用于低温甲烷干重整反应，研究在浸渍过程中添加甘氨酸对催化剂结构和甲烷干重整反应性能的影响。XRD、TEM和TPR表征结果表明，甘氨酸辅助浸渍法能够减小催化剂中NiO粒径，增强NiO与载体的相互作用，从而有利于在还原后催化剂中形成高分散、热稳定的Ni颗粒。在600 °C的甲烷干重整反应中，与普通浸渍法制备的Ni/SBA-15催化剂相比，甘氨酸辅助浸渍法制备的Ni/SBA-15-G催化剂活性和稳定性明显提高，且催化剂积碳量明显降低。Ni/SBA-15-G催化剂良好的催化性能归因于较小的Ni粒径。
关键词：甲烷干重整；CO2；Ni基催化剂；甘氨酸；高分散
中图分类号：X701 文献标识码：A
Highly Dispersed Ni/SBA-15 Catalyst Prepared by Glycine-assisted Impregnation Method for Low-temperature Dry Reforming of Methane YANG Ji-liang1, 2, LU Xin-kang1, 2, HAN Cui1, 2, LIU Hui3，GONG Dan-dan1, 2, WANG Lu-hui*1, 2 (1.Zhejiang Provincial Key Laboratory of Petrochemical Pollution Control, Zhejiang Ocean University, Zhoushan 316022, China; 2. School of Petrochemical Engineering and Environment, Zhejiang Ocean University, Zhoushan 316022, China; 3. School of Food and Pharmaceutical, Zhejiang Ocean University, Zhoushan 316022, China)
Abstract：The dry reforming of methane reaction can convert two greenhouse gases, methane and carbon dioxide, into more useful syngas, and nickel-based catalysts are considered to be one of the most promising catalysts for dry reforming of methane. In this paper, Ni/SBA-15 catalyst was used for low-temperature dry reforming of methane reaction, and the effect of adding glycine during the impregnation process on the catalyst structure and catalytic performance during dry reforming of methane was investigated. The results of XRD, TEM and TPR showed that the glycine-assisted impregnation method could reduce the NiO particle size and increase the interaction between NiO and the support, which is conducive to the formation of highly dispersed and thermally stable Ni particles in the reduced catalyst. During the dry reforming of methane reaction at 600 °C, the activity and stability of Ni/SBA-15-G catalyst prepared by glycine-assisted impregnation method were significantly higher than that of Ni/SBA-15 catalyst prepared by common impregnation method, and the amount of carbon deposition of the Ni/SBA-15-G catalyst was significantly less. The good catalytic performance of Ni/SBA-15-G catalyst was attributed to the small Ni particle size.
Key words：dry reforming of methane; CO2; Ni-based catalysts; glycine; highly dispersed
引用本文：杨继亮，鲁新康，韩翠，等.甘氨酸辅助浸渍法制备高分散Ni/SBA-15低温甲烷干重整催化剂研究[J]. 化学试剂，2022，44(12): 1789-1795。
【化学品与环境】
多氨基硅烷改性SBA-15分子筛对Cr3+的吸附性能研究
陈强强，齐迹，郭宇*，吴红梅
（辽宁工业大学 化学与环境工程学院，辽宁 锦州 121001）
摘要：以多氨基硅烷（NQ-62）为改性剂，采用后嫁接法制备了氨基改性的SBA-15介孔分子筛（SN-SBA-15）。利用扫描电子显微镜、透射电子显微电镜、能量色散X射线光谱、X-射线衍射、氮气吸附-脱附、热重、红外光谱等表征手段对样品的形貌、结构进行了分析。结果表明，与SBA-15相比较，SN-SBA-15的比表面积和孔径较小，但表面形貌和晶体结构没有明显改变。以SN-SBA-15为吸附剂，对水中Cr3+的吸附过程进行了动力学与热力学行为分析。研究表明，氨基改性过程可以显著增强SBA-15对Cr3+的吸附能力，当溶液初始pH值为6.0，吸附时间为390 min，其最大吸附量可达88.6 mg/g。SN-SBA-15对Cr3+的吸附过程符合准二阶动力学模型，吸附行为可以用Langmuir模型描述，吸附为自发、吸热、熵增加的过程。而且，SN-SBA-15重复再生后吸附性能较稳定，经过5次吸附与再生循环，吸附量仅降低了16.1%。
关键词：SBA-15分子筛；氨基；改性；吸附；Cr3+
中图分类号：O655.4 文献标识码：A 文章编号：0258-3283（2022）
Preparation of Muti-Amino Silane Functionalized SBA-15 Molecular Sieve for the Adsorption of Cr3+ from Aqueous Solution CHEN Qiang-qiang, QI Ji, GUO Yu*, WU Hong-mei (School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China)
Abstract: A novel amino-functionalized SBA-15 (SN-SBA-15) was synthesized by using post-grafting method, in which 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (NQ-62) was used as modified regent. The morphologies and structures of the samples were characterized by means of scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), nitrogen adsorption-desorption, thermal analysis (TGA) and fourier transform infrared spectra (FT-IR). In comparison with SBA-15, SN-SBA-15 exhibits a smaller BET surface area and pore size, but the modification process did not make significant surface morphology and crystal structure of SBA-15 change. The SN-SBA-15 was used to remove Cr3+ from the aqueous solution. The adsorption kinetics and thermodynamics were investigated. The results showed that amino functionalization of SBA-15 improved the adsorption capacity toward Cr3+. When the pH value was 6.0 and the contact time was 390 min, the maximum adsorption capacity was up to 88.6 mg/g. The kinetic and adsorption isotherms of Cr3+ ions on the SN-SBA-15 were correlated well with the pseudo-second-order mode and Langmuir isotherm model. Thermodynamic analysis indicated that the adsorption process was a spontaneous endothermic process of increased entropy. Moreover, SN-SBA-15 exhibited good reusability for application in the adsorption of Cr3+ ions, the adsorption capacity of SN-SBA-15 showed a loss of 16.1% after 5 cycles of adsorption and regeneration.
Key words: SBA-15 molecular sieve; amino groups; functionalization; adsorption; Cr3+ ions
引用本文：陈强强, 齐迹, 郭宇, 等. 多氨基硅烷改性SBA-15分子筛对Cr3+的吸附性能研究[J]. 化学试剂, 2022, 44(12):1796-1803.
PDMDAAC功能化二氧化钛复合材料对金属离子吸附研究
姚培1, 李树白*1，张启蒙1，刘媛1，王鲁超2，秦建国*3
(1. 常州工程职业技术学院 化工与制药工程学院，江苏 常州 213164；2. 常州大学 石油工程学院，江苏 常州 213164；3. 上海沃凯生物技术有限公司，上海 201506）
摘要：以钛酸四丁酯为前驱体，聚二甲基二烯丙基氯化铵（PDMDAAC）为改性剂，采用凝胶-溶胶法制备功能化二氧化钛，通过XRD、SEM和BET等方法对其性能进行表征。以金属离子Al3+、Cr3+、Cu2+、Pb2+为研究对象，研究了不同掺杂比及不同吸附参数对吸附率的影响。结果表明，当PDMDAAC物质的量比为钛酸四丁酯的0.2%时，20℃、pH 8.5、离子强度取NaCl质量浓度10%、10 mg功能化二氧化钛处理100 mg/L的混合废水中，5 min之内Al3+、Cr3+去除率可以达到99%以上，属于快吸附。Cu2+、Pb2+在50 min达到吸附平衡，去除率为99.5%，符合准二级动力学模型。混合金属离子的吸附存在竞争吸附。功能化二氧化钛重复可使用8次，吸附率仍能保持在84%以上。
关键词：聚二甲基二烯丙基氯化铵；二氧化钛；金属离子；掺杂；吸附
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2022）12--
Adsorption of metal ions by polydimethyldiallyl ammonium chloride functionalized titanium dioxide composite materials YAO Pei1, LI Shu-bai*,1 ZHANG Qi-meng1, LIU Yuan1, WANG Lu-chao2, QIN Jian-guo*3 (1. School of Chemical and Pharmaceutical Engineering, Changzhou Vocational Institute of Engineering, Changzhou 213164, China；2. School of Petroleum Engineering, Changzhou University, Changzhou 213164, China; 3. Shanghai Our ChemBio-Technology Co., Ltd., Shanghai 201506, China)
Abstract: Tetra-butyl titanate was used as the precursor, the strong cationic electrolyte polydimethyldiallyl ammonium chloride (PDMDAAC) was used as a modifier, and PDMDAAC functionalized titanium dioxide was prepared by the gel-sol method. The properties of functionalized titanium dioxide were achieved by means of XRD, SEM and BET. The simulated wastewater of metal ions Al3+ Cr3+ Cu2+ and Pb2+ were the research objects, and the effects of different doping ratios and different adsorption parameters on the adsorption rate were studied. The results showed that the removal rate of Al3+ and Cr3+ could reach more than 99% within 5 min, when the molar ratio of PDMDAAC was 0.2% of tetra-butyl titanate, pH was 8.5, ionic strength was 10%, the dosage of functionalized titanium dioxide was 10 mg, and the mixed wastewater concentration of metal ion was 100mg/L. The adsorption equilibrium of Cu2+ and Pb2+ reached at 50min, and the corresponding removal rate was 99.5%, the kinetic model of which fitted with the pseudo-second-order model. During adsorption process, the adsorption of mixed metal ions has competitive adsorption. Functionalized TiO2 can be reused for 8 times, and its adsorption rate is still above 84%.
Key words: Polydimethyldiallyl ammonium chloride; titanium dioxide; metal ion; doped; adsorption
引用本文：姚培，李树白，张启蒙，等. PDMDAAC功能化二氧化钛复合材料对金属离子吸附研究[J]. 化学试剂，2022，44(12)：1804-1809 .
【标准物质与标准品】
润滑油中元素检测方法及标准研究进展
屈小梭1，李硕*2，谢琼1，杜彪3，李庆武2
(1. 中国环境科学研究院，国家环境保护机动车污染控制与模拟重点实验室，北京 100012；
2. 中国计量科学研究院，北京 100029；
3. 北京易兴元石化科技有限公司，北京 101301)
摘要：由于发动机等机械磨损维修费用很高，因此建立发动机和机械正常运转条件的判断方法，以便监控其运转状态十分必要。测定润滑油中磨损元素含量变化是设备状态监测工作正常与否的一项重要诊断方法。可用于预判早期的机械磨损。污染物元素浓度的显著增加表明润滑油中可能混入外来物质，这些物质会导致设备的磨损或润滑油的衰变降解。研究润滑油中金属和污染物元素含量随时间和工作强度的变化规律，有助于必要时采取相应的措施，避免灾难性事故的发生。综述了润滑油中元素检测的研究现状及进展，梳理了国内外有关标准方法的制修订状况，以期为润滑油中元素检测方法的创新及标准的及时更新提供思路。
关键词：润滑油；检测方法；行业标准；磨损金属；污染物元素
中图分类号：TQ646.1 文献标识码：A 文章编号：0258-3283(2022) --
Research progress on detection methods and standards of elements in lubricating oil QU Xiao-suo1, LI Shuo*2, XIE Qiong1, DU Biao3, LI Qing-wu2 (1. State Environmental Protection Key Laboratory of Vehicle Emission Control and Simulation, Chinese Research Academy of Environmental Sciences, Beijing 100012,China；2. National Institute of Metrology, Beijing 100029, China；3. Beijing Yixingyuan Petrochemical Technology Co., Ltd，Beijing 101301, China)
Abstract: Since the maintenance cost of the engine and other machinery is very high after mechanical wear, it is necessary to establish a judgment method for the normal operating conditions of the engine and the machinery to monitor its operating state. Determining the change in the content of wear elements in lubricating oil is an important diagnostic method to monitor whether the working state of the equipment is normal, and can be used to predict the early mechanical wear. Early wear can be predicted by comparing the presence or abnormal concentration growth of wear metals with baseline concentration data. The significant increase in the concentration of contaminant elements indicated that the lubricating oil may be mixed with foreign substances, which can cause the wear of equipment or the decay and degradation of the lubricating oil. By capturing the trend in metal and pollutant elements content over time and work intensity, corresponding measures can be taken when necessary to help avoid the occurrence of catastrophic accidents. The research progress of element detection in lubricating oil was reviewed, and the formulation and revision of relevant domestic and international standard methods was sorted out, so as to provide ideas for the innovation of element detection methods and the timely update of standards in lubricating oil.
Key words: lubricating oil; testing method; industry standard; wear metals; contamination element
引用本文：屈小梭，李硕，谢琼，等. 润滑油中元素检测方法及标准研究进展[J]. 化学试剂, 2022, 44(12): 1810-1816。
2,4-二氯苯氧乙酸纯度标准物质定值方法及不确定度评估
吴雨芯1,2，王敏1，刘亚轩2，刘权辉1，周剑1，王彤彤1，杨梦瑞*1
（1.中国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重点实验室，北京 100081；2.天津农学院，食品科学与生物工程学院，天津 300380）
摘要：研制2,4-二氯苯氧乙酸纯度标准物质。采用质量平衡法和氢谱定量核磁法对2,4-二氯苯氧乙酸纯度标准物质候选物进行纯度定值，对主组分影响较大的水分含量采用卡尔费休法准确测量。对2,4-二氯苯氧乙酸纯度标准物质进行了均匀性检验、稳定性考察以及不确定度评估。2,4-二氯苯氧乙酸纯度标准物质的纯度值为99.6%，扩展不确定度为0.2%（k=2），水分含量为0.291%，特性量值均匀性良好，12个月内稳定性可靠。2,4-二氯苯氧乙酸纯度标准物质符合国家有证标准物质条件并获得国家一级标准物质认定，编号为GBW09291。
关键词：2,4-二氯苯氧乙酸；纯度标准物质；定量核磁法；质量平衡法
中图分类号： 文献标识码：A 文章编号：0258-3283（2022）--
Development of a purity certified reference material of 2,4-Dichlorophenoxyacetic acid WU Yu-xin1,2, WANG Min1, LIU Ya-xuan2, LIU Quan-hui1, ZHOU Jian1, WANG Tong-tong1, YANG Meng-rui*1 (1. Institute of Quality Standard and Testing Technology for Agro-Products of CAAS, Key Laboratory of AgO-Product Quality and Safety, Chinese Academy of Agricultural Sciences, Beijing 100081, China; 2. Faculty of Food Science and Bioengineering, Tianjin Agricultural University, Tianjin 300380, China)
Abstract: This study aims to develop purity reference material of 2,4-dichlorophenoxyacetic acid. Purity rating of 2,4-dichlorophenoxyacetic acid purity reference standard candidate was performed by mass balance method and 1H NMR-based quantitative method, while the moisture content that has a large impact on the main component was accurately measured by Karl Fischer method. The purity reference standard 2,4-dichlorophenoxyacetic acid was subjected to homogeneity study, stability studies, and uncertainty assessments. The purity value of the 2,4-dichlorophenoxyacetic acid standard material was 99.6%, the expansion uncertainty was 0.2% (k=2), the moisture content was 0.291%, the characteristic value was uniform, and the stability was reliable within 12 months. The purity standard 2,4-dichlorophenoxyacetic acid met the conditions of the national certified standard substance and had been recognized as a national first-class standard substance, numbered GBW09291.
Key words: 2,4-dichlorophenoxyacetic acid; purity reference material; 1HNMR-based quantitative method; mass balance method
引用本文：吴雨芯，王敏，刘亚轩，等. 2,4-二氯苯氧乙酸纯度标准物质定值方法及不确定度评估[J]. 化学试剂, 2022, 44(12): 1817-1823。
降糖类口服液甲苯磺丁脲等5种非法添加物基体标准物质的研制
时玲，国振，赵光亮，李秀琴*，张庆合
（中国计量科学研究院 化学计量与分析科学研究院，北京 100029）
摘要：采用添加法制备了降糖类口服液中甲苯磺丁脲、马来酸罗格列酮、格列本脲、格列喹酮和瑞格列奈基体标准物质候选物；建立了高效液相色谱方法准确定值方法，甲苯磺丁脲、马来酸罗格列酮、格列本脲、格列喹酮、瑞格列奈的加标回收率分别为100.3% ~ 104.8%、94.4% ~ 102.9%、90.9% ~ 104.7%、96.2% ~ 104.0%、96.6% ~ 103.1%，RSD依次为1.0% ~ 3.1%、1.0% ~ 1.9%、0.6% ~ 1.0%、1.1% ~ 2.6%、0.7% ~ 1.7%；标准物质均匀性和稳定性均良好。并对该标准物质的不确定度进行系统评估，定值结果为：甲苯磺丁脲（63.6 ± 1.1） mg/kg、马来酸罗格列酮（42.2 ± 1.2） mg/kg、格列本脲（22.6 ± 0.7） mg/kg、格列喹酮（19.7 ± 0.6） mg/kg、瑞格列奈（60.0 ± 1.5） mg/kg，扩展因子k = 2。该标准物质可用于食品检测实验室相关项目的方法开发、日常检测质量控制、以及实验室能力验证等领域，保证实验室检测数据质量，提升检测能力。
关键词：降糖类口服液；标准物质；非法添加物；高效液相色谱法；不确定度评估
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2022）
Development of Matrix Reference Material of 5 Illegal Additives Such As Tolbutamide in Hypoglycemic Oral Liquid SHI Ling, GUO Zhen, ZHAO Guang-liang, LI Xiu-qin*, ZHANG Qing-he (Division of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, China)
Abstract: This study developed matrix reference material (RM) candidates of tolbutamide, rosiglitazone maleate, glibenclamide, gliquidone, and repaglinide in hypoglycemic oral liquid using an additive method. A high performance liquid chromatography (HPLC) method for determining quasi-deterministic values was established. The spiked recoveries of tolbutamide, rosiglitazone maleate, glibenclamide, gliquidone and repaglinide were 100.3% ~ 104.8%, 94.4% ~ 102.9%, 90.9% ~ 104.7%, 96.2% ~ 104.0% and 96.6% ~ 103.1%, respectively, with corresponding RSDs of 1.0% ~ 3.1%, 1.0% ~ 1.9%, 0.6% ~ 1.0%, 1.1% ~ 2.6% and 0.7% ~ 1.7%. The reference materials have good homogeneity and stability. The uncertainties of the RM candidates were systematically evaluated to be: tolbutamide (63.6 ± 1.1) mg/kg, rosiglitazone maleate (42.2 ± 1.2) mg/kg, glibenclamide (22.6 ± 0.7) mg/kg, gliquidone (19.7 ± 0.6) mg/kg, and repaglinide (60.0 ± 1.5) mg/kg, with an extension factor k = 2. The RMs developed could be applied in methods development, quality control, and verification for food testing laboratories to improve accuracy and enhance measurement capability.
Key words: hypoglycemic oral liquid; reference material; illegal addition; HPLC; uncertainty evaluation
引用本文：时玲, 国振, 赵光亮, 等. 降糖类口服液甲苯磺丁脲等5种非法添加物基体标准物质的研制[J]. 化学试剂, 2022, 44(12)：1824-1829.
监测环境空气醛酮用溶液标准样品的研制
杨刚1,2，赵亚娴*1,2，黄林艳1,2，赵彦辉1,2，田中男1,2
（1. 生态环境部环境发展中心环境标准样品研究所，北京 100029；
2. 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: 为满足环境空气中醛酮类化合物分析监测质量要求，针对我国目前未有醛酮类溶液有证标准样品的现状，研制了乙腈中13种醛酮类混合溶液标准样品。通过研究高纯原料中主成分含量、水分和无机元素等杂质，利用质量平衡法确定纯度，使用高纯衍生物质制备以醛酮化合物质量计的混合溶液标准样品。研究建立了高效液相色谱法，对样品的均匀性、稳定性及标准值进行不确定度评估。结果表明，醛酮衍生物纯度为99.45% ~ 100%，研制的乙腈中13种醛酮类混合溶液标准样品均匀性良好，在18个月冷藏保存条件下量值稳定，标准样品特性量值为10.0 μg/mL，相对扩展不确定度为1.8% ~ 4.6%。该标准样品可用于环境空气中醛酮类化合物分析监测的质量控制和质量保证。
关键词：醛酮；衍生物；标准样品；均匀性；稳定性
中图分类号：X831 文献标识码：A 文章编号：0258-3283（2022）
Development of Aldehyde Ketone Solution Reference Material for Ambient Air Monitoring YANG Gang1,2, ZHAO Ya-xian*1,2, HUANG Lin-yan1,2, ZHAO Yan-hui1,2, TIAN Zhong-nan1,2 (1. Institute far Environmental Reference Materials, Environmental Development Centre of the Ministry of Ecology and Environment, Beijing 100029; 2. State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Beijing 100029)
Abstract: In order to meet the quality requirements for the analysis and monitoring of aldehyde ketone in the ambient air, 13 kinds of Aldehyde Ketone certified reference material in acetonitrile were developed in view of the lack of related CRM in China. The purity of Aldehyde Ketone derivative was analyzed by mass balance method, and impurities such as principal component analogs, water, and inorganic elements in pure raw materials were detected. Preparing the solution reference material was based on the mass of Aldehyde Ketone compounds with high-purity derivatives. The analysis method of high-performance liquid chromatography was built, which was used to assess the homogeneity, stability, and the standard values of the samples. The results showed that the purity of Aldehyde Ketone derivative was 99.45% ~ 100%, the value of which were rather stable at 4 ℃ for 18 months. The characteristic value of the reference material was 10.0 μg/mL, and the relative extended uncertainty was 1.8% ~ 4.6%. These 13 kinds of Aldehyde Ketone in acetonitrile solution reference material can be used for quality control and quality assurance in analyzing and monitoring aldehydes and ketones in ambient air.
Key words: Aldehyde Ketone; derivatives; solution certified reference; homogeneity; stability
引用本文：杨刚, 赵亚娴, 黄林艳, 等. 监测环境空气醛酮用溶液标准样品的研制[J]. 化学试剂, 2022, 44(12):1830-1837.
【合成与工艺技术】
2,5-二特辛基对苯二酚合成工艺研究
沈京华1，张念椿*1，薛冰凡2，郑鹤立1
（1. 西陇科学股份有限公司，广东 广州 510535；2. 达高工业技术研究院(广州)有限公司，广东 广州 510535）
摘要：2,5-二特辛基对苯二酚是一种性能优良的酚类抗氧化剂，选用三氟甲磺酸作为催化剂，催化二异丁烯与对苯二酚的傅克烷基化反应来进行合成。比较了三氟甲磺酸与硫酸、磷酸的催化性能，结果表明三氟甲磺酸在较低的催化剂浓度下即表现出较高的催化活性，反应物转化率高且体系副反应程度较低，反应条件温和，并且不会产生大量酸性废水。对反应条件进行了优化，研究了原料配比、催化剂用量、反应温度、反应时间等工艺条件对反应结果的影响。通过洗涤与重结晶的方法对反应粗品进行了提纯，研究了不同溶剂及比例对重结晶回产率与产物纯度的影响，确认最佳溶剂配比为V(石油醚)∶V(乙酸乙酯)=20∶1，产品纯度达到99.2%。最适宜的反应条件为：反应温度：60 ℃，反应时间：4 h，n（酸）∶n（酚）=0.01∶1，n（烯）∶n（酚）=2.6∶1，产率90.2%。
关键词：烷基化；2,5-二特辛基对苯二酚；三氟甲磺酸；重结晶；合成；
中图分类号：TQ243.1 文献标识码：A 文章编号：0258-3283（2022）--
Study on synthesis technology of 2,5-di-tert-octyl hydroquinone SHEN Jing-hua1, ZHANG Nian-chun*1, XUE Bing-fan2 (1. Xilong Scientific Co., Ltd., Guangzhou 510535, China; 2. Dagao Industrial Technology Research Institute (Guangzhou) Co., Ltd., Guangzhou 510535, China)
Abstract: 2,5-di-tert-octyl hydroquinone is a good phenolic antioxidant. Trifluoromethanesulfonic acid was used as a catalyst to catalyze the Friedel-Crafts alkylation of diisobutene and hydroquinone for synthesizing 2,5-di-tert-octyl hydroquinone. Under the same conditions, the catalytic performance of trifluoromethanesulfonic acid was compared with sulfuric acid and phosphoric acid. The results showed that trifluoromethanesulfonic acid exhibited higher catalytic activity at lower catalyst concentration and high reactant conversion. And the reaction was performed under mild condition with few side products and did not produce a large amount of acidic wastewater. The reaction conditions were optimized by investigating the effects of raw material ratio, catalyst dosage, reaction temperature and reaction time on the reaction results. Moreover, the crude product was purified by washing and recrystallization. The effects of different solvents and ratios on the recrystallization recovery and product purity were studied. It was confirmed that the best solvent ratio was V (petroleum ether): V (ethyl acetate) = 20: 1, and the product purity reached 99.2%. The optimum reaction conditions were as follows: reaction temperature: 60 ℃, reaction time: 4 h, n (acid): n (phenol) = 0.01:1, n (ene): n (phenol) = 2.6:1, and the yield was 90.2%.
Key words: Friedel-Crafts alkylation; 2,5-di-tert-octyl hydroquinone; trifluoromethanesulfonic acid; recrystallization; synthesis;
引用本文：沈京华，张念椿，薛冰凡.，等. 2,5-二特辛基对苯二酚合成工艺研究[J]. 化学试剂, 2022, 44(12): 1838-1842。
噻唑联苯并呋喃衍生物的设计、合成及活性研究
谢珺a,b，苗菁a，崔杏a,b，王建塔a,b，王聪*a,b，汤磊*a,b
（贵州医科大学 a. 药学院，贵州 贵阳 550004；b. 贵州省化学合成药物研发利用工程技术研究中心，贵州 贵阳 550004）
摘要：黄嘌呤氧化酶是治疗高尿酸血症、痛风等相关疾病的重要靶点。通过对非布索坦的构效关系的分析，并基于药物化学的拼合原理，将非布索坦的噻唑环和苯溴马隆的苯并呋喃环拼合，设计合成了12个化合物，结构经过1HNMR、13CNMR和HRMS鉴定。对目标化合物进行黄嘌呤氧化酶的活性测试，2-(2-乙基-5-氟苯并呋喃-3-乙基)-4-甲基-5-噻唑甲酸具有相对较好的活性。分子对接的结果说明2-(2-乙基-5-氟苯并呋喃-3-乙基)-4-甲基-5-噻唑甲酸与黄嘌呤氧化酶的相互作用和非布索坦相似。该化合物结构可以进步优化，为黄嘌呤氧化酶抑制剂的提供候选化合物。
关键词：非布索坦；黄嘌呤氧化酶抑制剂；痛风；设计；生物活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2022）--
Design，synthesis and activity study of thiazole linking benzofuran derivatives XIE Juna,b, MIAO Jinga, CUI Xinga,b, WANG Jian-taa,b, WANG Cong*a,b, TANG Lei*a,b (a. College of Pharmacy, b. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R & D, Guizhou Medical University, Guiyang 550004, China)
Abstract: Xanthine oxidase is an important target for the treatment of hyperuricemia, gout, and other related diseases. Based on the analysis of the structure-activity relationship of febuxostat and the principle of pharmaceutical chemistry, 12 compounds were designed and synthesized by combining the thiazole ring of febuxostat with the benzofuran ring of benbromarone, and their structures were identified by 1HNMR, 13CNMR and HRMS spectra. Moreover, the xanthine oxidase activities of the target compounds were tested, and the results showed that 2-(2-ethyl-5-fluorobenzofuran-3-ethyl)-4-methyl-5-thiazole carboxylic acid had the good activity. Molecular docking results revealed that the interaction between 2-(2-ethyl-5-fluorobenzofuran-3-ethyl) -4-methyl-5-thiazole carboxylic acid and xanthine oxidase was similar to febuxostat. In future, this structure can be further optimized as an candidate for xanthine oxidase inhibitor.
Key words：febuxostat; xanthine oxidase inhibitor; gout; design; biological activity
引用本文：谢珺，苗菁，崔杏，等. 噻唑联苯并呋喃衍生物的设计、合成及活性研究[J]. 化学试剂, 2022, 44(12): 1843-1848。
