【综述与专论】
磁性水凝胶的制备及其应用研究进展
董黎明，陈金雨，袁源，王士凡*
（徐州工程学院 材料与化学工程学院，江苏 徐州 221018）
摘要：近些年来，磁性水凝胶材料因其优异的磁性、稳定性和良好的生物相容性而备受关注。同时，对磁性水凝胶的材料改性工作也在不断推进，以提高磁性水凝胶材料的吸附、运载等特定能力。介绍了磁性水凝胶材料的制备，包括共混法、接枝法、原位沉淀法和溶胀法。重点介绍了其在重金属离子吸附、药物运输、癌症治疗等领域的应用。考虑到对未来发展的贡献，对磁性水凝胶在智能多功能材料方面的应用进行了展望。
关键词：磁性水凝胶；吸附；水处理；生物医学
中图分类号：O032.63 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0522
Progress in the Preparation and Application of Magnetic Hydrogels DONG Li-ming, CHEN Jin-yu, YUAN Yuan, WANG Shi-fan* (School of Materials and Chemical Engineering, Xuzhou Institute of Engineering, Xuzhou, 221018, China)
Abstract: In recent years, magnetic hydrogels have attracted much attention because of their excellent magnetism, stability and good biocompatibility. At the same time, the modification of magnetic hydrogels is also being carried out constantly to improve the adsorption, transport and other specific capabilities of magnetic hydrogels. In the paper, the preparation of magnetic hydrogel materials is introduced, and its application and effect in the fields of heavy metal ion adsorption, drug transportation and cancer treatment are highlighted. The main methods can be classified as blending method, grafting method, in situ precipitation, and swelling method. Overall, in view of the contributions in the future developments, this review summarized the progress of magnetic hydrogels in the field of smart multifunctional materials.
Key words: magnetic hydrogel; adsorption; water treatment; biomedical.
引用本文：董黎明，陈金雨，袁源，等. 磁性水凝胶的制备及其应用研究进展[J]. 化学试剂, 2023, 45(2): 1-10。
香豆素类杂环化合物的抗微生物活性研究进展
彭莘媚*，王江河，贺银菊，李云萍，陈汉生，慈成刚
(黔南民族师范学院 化学化工学院，贵州 都匀 558000)
摘要：香豆素母核反应活性高，结构修饰性强，易引入多种官能团实现结构多样化，在医药、农药、香料、材料等多种领域具有较高的应用价值。杂环修饰的香豆素类化合物具有广泛的生物活性、多靶点的作用机制、更强的选择性及更低的毒性等特点，在医药领域的研究一直是研究者们关注的热点。随着微生物耐药性的加剧，寻找有效且不易引起菌株产生耐药性的抗感染药物迫在眉睫。综述了近5年来香豆素类杂环化合物在抗细菌、抗结核及抗真菌3个方面的生物活性研究概况，以期为相关研究提供参考。
关键词：香豆素；杂环化合物；抗细菌；抗结核；抗真菌
中图分类号：R914.4 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0632
Recent Progress on the Antimicrobial Activities of Coumarin-derived Heterocyclic Compounds PENG Xin-mei*, WANG Jiang-he, HE Yin-ju, LI Yun-ping, CHEN Han-sheng, CI Cheng-gang (School of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China)
Abstract: Coumarin core has high chemical reactivity. It is much easy to be introduced into a variety of functional groups to achieve its derivatives with different applications, which are widely used in medicine, pesticides, spices, materials and other fields. Coumarins modified by heterocycles possess diverse biological activities, multi-targets mechanism, stronger selectivity and lower toxicity. These advantages make them become the focus for researchers in medicine field. With the rapid increase of microbial resistance, it is urgent to search for effective anti-infective drugs with no or little resistance. The present review aimed to highlight the current progress on the antibacterial, antituberculotic and antifungal activities of coumarin heterocyclic compounds in the past five years. It is hopeful to provide reference for future exploration.
Key words: coumarin; heterocyclic compound; antibacterial; antituberculotic; antifungal
引用本文：彭莘媚，王江河，贺银菊，等. 香豆素类杂环化合物的抗微生物活性研究进展[J]. 化学试剂, 2023, 45(2): 11-21。
天然二氢黄酮醇类化合物及其衍生物的研究进展
刘懿锋，林汝娟，周琢强*
（华南农业大学 材料与能源学院，广东 广州 510642）
摘要：二氢黄酮醇即3-羟基二氢黄酮，在植物界中广泛存在，是黄酮类化合物的重要组成部分，具有抗氧化、抗病毒、抗肿瘤、抗菌等多种生物活性，备受医药、食品等多个领域的关注。二氢黄酮醇类化合物的生物活性与其结构具有紧密的联系，通过结构修饰还可改善或改变其活性。因此对二氢黄酮醇类化合物结构、生物活性及结构修饰等方面进行综述，期望为其今后的进一步开发提供帮助。
关键词：二氢黄酮醇；生物活性；结构修饰；研究进展；衍生物
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0697
Progress in Natural Products and Derivatives of Flavanonol LIU Yi-feng , LIN Ru-juan , ZHOU Zhuo-qiang* (College of Materials and Energy, South China Agricultural University, Guangzhou 510642, China)
Abstract: Flavanonol, namely 3-hydroxyflavanone, widely exists in the plant kingdom and is an important part of flavonoid. It has various biological activities such as antioxidant, antiviral, antitumor and antibacterial, and has attracted much attention in many fields such as medicine and food. The biological activity of flavanonols is closely related to their structure, and their activity can be improved or changed by structural modification. Therefore, the structure, biological activity and structural modification of flavanonols were reviewed in this paper, hoping to support their further development.
Key words: flavanonol; biological activities; structural modification; research progress; derivatives
引用本文：刘懿锋, 林汝娟, 周琢强. 天然二氢黄酮醇类化合物及其衍生物的研究进展[J]. 化学试剂, 2023, 45（2）：22-32.
【生化与药用试剂】
李林博1，刘玉肖1，樊平平1，周淑晶1,2，李进京*1,2
（1.佳木斯大学 药学院，黑龙江 佳木斯 154007；2.黑龙江省药学研究所，黑龙江 佳木斯 154007）
摘要：天然产物查尔酮因其具有广泛的生物活性而被人们所关注。特别是在抗肿瘤方面，可作用于多种抗癌靶标从而发挥抗肿瘤作用，如EGFR、VEGFR-2、Ntoch信号通路、PI3K/AKT信号通路、WNT/β-cantenin信号通路以及线粒体介导的细胞凋亡信号通路等。依据不同抗癌机制对近年来查尔酮及其衍生物在抗肿瘤活性方面的研究成果进行分类阐述，为新型含α, β-不饱和酮结构的抗肿瘤药物的研发工作提供参考。
关键词：查尔酮；天然产物；抗癌靶标；抗肿瘤活性；研究进展
中图分类号：R979.1 文献标识码：A 文章编号：
DOI: 10.13822/j.cnki.hxsj.2022.0450
Research Progress on Anti-tumor Activity of Chalcone Derivatives LI Lin-bo1, LIU Yu-xiao1, FAN Ping-ping1, ZHOU Shu-jing1,2, LI Jin-jing*1,2 (1. College of Pharmacy, Jiamusi University, Jiamusi 154007, China；2.Heilongjiang Institute of Pharmacy，Jiamusi 154007, China)
Abstract: Chalcone as the natural product has attracted people's attention due to its diverse biological activities. Especially in terms of anti-tumor effect, it can bind to a variety of anti-cancer targets, such as EGFR, VEGFR-2, Ntoch signaling pathway, PI3K/AKT signaling pathway, WNT/β-cantenin signaling pathway and mitochondrial-mediated apoptosis signaling pathway. Classified by anti-cancer mechanism, the account is mainly focused on the research of chalcone derivatives in anti-tumor field in the last years, in order to provide references in the development of novel anti-tumor drugs containing α, β -unsaturated ketone structure.
Keywords: chalcone; natural product; anticancer target; antitumor activity; research progress
引用本文：李林博，刘玉肖，樊平平，等. 查尔酮类化合物抗肿瘤活性研究进展[J]. 化学试剂, 2023, 45(2): 33-42。
酪氨酸激酶2抑制剂的研究进展
姚华良，曾宪霞，张洁，黄怀征，何林洪*
(广西医科大学 药学院 ，广西 南宁 530021)
摘要：酪氨酸激酶2（TYK2）作为两面神激酶非受体酪氨酸激酶家族的一员，被IL-12、IL-23和I-IFN等多种细胞因子激活，启动信号转导及转录激活因子（STAT）将信号传递到细胞核内，启动炎症免疫反应，参与多种慢性炎症和自身免疫性疾病进展。目前，关于TYK2抑制剂的报道逐渐增多，主要靶向该蛋白的激酶结构域（JH1）和假激酶结构域（JH2），前者为ATP竞争性抑制剂，后者为变构调节剂。由于变构抑制剂的结合位点为非ATP竞争结构域，可较容易地获得激酶选择性以下调不良反应的发生，同时减少氨基酸突变所造成的耐药问题，因此，该类抑制剂正逐渐被科研工作者青睐。从TYK2结构特点出发，分别介绍靶向JH1和JH2的抑制剂，为以后的研究提供参考。
关键词：酪氨酸激酶2；激酶结构域（JH1）；ATP竞争性抑制剂；假激酶结构域（JH2）；变构调节剂
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0462
Research Progress of Tyrosine Kinase 2 Inhibitors YAO Hua-liang, ZENG Xian-xia, ZHANG Jie, HUANG Huai-zheng, HE Lin-hong* (College of Pharmacy, Guangxi Medical University, Nanning 530021, China)
Abstract: Tyrosine kinase 2 (TYK2), a member of Janus Kinases (JAKs) belongs to the family of non-receptor tyrosine kinases, can be activated by many cytokines including IL-12, IL-23 and I-INF, then trigger the signal transduction and transcriptional activation factors (STATs) to transfer the signals into nucleus, initiate inflammatory immune responses and participate in the progressions of various chronic inflammatory and autoimmune diseases ultimately. At present, the research about TYK2 inhibitors that mainly target its kinase domain (JH1) and pseudokinase domain (JH2) are gradually increasing, the former ones are ATP-competitive inhibitors, while the latter ones are allosteric modulators. Given that the binding site of TYK2 allosteric inhibitors is not the ATP-competitive domain, which can easily obtain the kinase selectivity and reduce the appearance of adverse reactions, as well as cut down the risk of drug resistance caused by amino acid mutations, they are gradually getting attention by researchers. This paper summarizes inhibitors targeting JH1 and JH2 respectively according to its structure, which may provide reference for the future research.
Key words: TYK2; kinase domain (JH1); ATP-competitive inhibitors; pseudokinase domain (JH2); allosteric modulators
引用本文：姚华良，曾宪霞，张洁，等. 酪氨酸激酶2抑制剂的研究进展[J]. 化学试剂, 2023, 45(2): 43-53。
基于丁酸功能化基团钌化合物的合成及其抗菌活性研究
曾威*，丁云霞，姜雯雯，陈晓燕，荣小娟，马兆霞
(江西科技学院 医学院，江西 南昌 330013)
摘要：以含丁酸取代的邻菲啰啉衍生物为主配体(PHIBA)合成了两个新型抗菌钌化合物[Ru(dtb)2PHIBA](PF6)2 (Ru1)、[Ru(dmb)2PHIBA](PF6)2 (Ru2)，通过最低抑菌浓度、时间杀伤曲线、溶血毒素试验、棋盘联用实验等评价了钌化合物对金黄色葡萄球菌的抗菌活性。采用DAPI/PI染色试验、(DISC3)5膜去极化染色试验、DNA泄露试验、内膜渗透性实验及活性氧监测(DCFH-DA)试验验证了化合物Ru1的抑菌机制。最后通过大蜡螟幼虫感染模型研究了Ru1的体内抗菌活性。结果表明，两个钌配合物均具有显著的抗菌活性(MIC=1.56 ~ 6.25 μg/mL)，钌化合物Ru1 (1.56 μg/mL)能通过破坏细菌细胞膜并诱导产生ROS杀死细菌。此外，Ru1不仅能有效抑制细菌毒素的分泌，而且与部分抗生素具有协同抗菌活性(FICI≤0.5)。更为重要的是Ru1能显著提高细菌感染后大蜡螟幼虫的存活率(40%)。研究结果表明，基于丁酸功能化配体的钌化合物具有显著的抗菌活性。
关键词：钌配合物；丁酸；抗菌机制；金黄色葡萄球菌
中图分类号：R916 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0624
Ruthenium Complex Based on Butyric Acid Functionalized Ligand：Synthesis and Antibacterial Activity Study ZENG Wei*, DING Yun-xia, JIANG Wen-wen, CHEN Xiao-yan, RONG Xiao-juan, MA Zhao-xia (School of Medicine, Jiangxi University of Technology, Nanchang, 330013, China)
Abstract: Two ruthenium complexes based on butyric acid functionalized ligand: [Ru(dtb)2PHIBA](PF6)2 (Ru1)、[Ru(dmb)2PHIBA](PF6)2 (Ru2), were synthesized and characterized. Their antibacterial activity against Staphylococcus aureus were investigated through time-kill kinetics assay, rabbit erythrocyte hemolysis assays and checkerboard assay. In addition, DAPI/PI staining assay, membrane depolarization assay, DNA leakage assay and ROS generation monitored assay were employed to explore the antibacterial mechanism. At last, the antibacterial activity of Ru1 in vivo was studied using Galleria mellonella. The results indicated that two ruthenium complexes exhibited strong antibacterial activity against Staphylococcus aureus (MIC=1.56 ~ 6.25 μg/mL). The most active complex Ru1 (1.56 μg/mL) kill bacteria through destroying bacterial cell membranes and inducing the generation of ROS. In addition, Ru1 could inhibit the toxin secretion and showing synergistic effect (FICI≤0.5) when used in combination with some antibiotics. More importantly, Ru1 also effective in vivo. In summary, ruthenium complex based on butyric acid functionalized ligand are promising antibacterial agents.
Key Words: ruthenium complexes; butyric acid; antibacterial mechanism; Staphylococcus aureus
引用本文：曾威，丁云霞，姜雯雯，等. 基于丁酸功能化基团钌化合物的合成及其抗菌活性研究[J].化学试剂，2023,45（2）：54-61.
2-(2-氨基苯基)苯并咪唑铂(II)配合物的合成及其与BSA作用的光谱研究
袁涛，覃姣兰*，罗翠萍，仇继家，钟雨佳，姚鹏飞
(百色学院 化学与环境工程学院 广西城市水环境重点实验室，广西 百色 533000)
摘要：以2-(2-氨基苯基)苯并咪唑(L2)和K2PtCl4为原料反应合成铂配合物[Pt(L2)2Cl2]•H2O (L2-Pt)，并获得其晶体结构。在生理条件下(pH 7.40），利用紫外吸收光谱、荧光光谱研究 L2和L2-Pt对牛血清白蛋白（BSA）相互作用的影响。结果表明，L2和L2-Pt通过静态猝灭方式引起BSA荧光发生猝灭，在298、304、310 K这3个温度下，L2-Pt对BSA的猝灭率及猝灭常数均大于L2。焓变(∆H)、熵变(∆S)和吉布斯自由能变化（△G）表明，L2与BSA间的作用力主要是疏水力(△H>0、△S>0)，结合是自发进行的（△G＜0）；而L2-Pt与BSA间的作用力主要是氢键和范德华力(△H＜0、△S＜0)，结合也是自发进行的（△G＜0）。紫外-可见光谱和同步荧光表明L2-Pt并未使BSA的微结构发生改变。
关键词：铂配合物；牛血清白蛋白；荧光光谱；相互作用；静态猝灭
中图分类号：0657 文献标识码：A 文章编号：
DOI: 10.13822/j.cnki.hxsj.2022.0633
Synthesis of 2-(2-Aminophenyl) Benzimidazole Platinum Complex and Spectral Study of its Interaction with BSA YUAN Tao, QIN Jiao-lan*,LUO Cui-ping , QIU Ji-jia, ZHONG Yu-jia, YAO Peng-fei ( Guangxi Key Laboratory of Urban Water Environment, College of Chemical and Environmental Engineering, Baise University，Baise 533000，China)
Abstract: The platinum complex [Pt(L2)2Cl2]•H2O(L2-Pt) was synthesized from 2-(2-aminophenyl)benzimidazole(L2) and K2PtCl4 as raw materials. The corresponding crystal structure was obtained. The effect of L2 and L2-Pt to bovine serum albumin (BSA) was studied by UV absorption, fluorescence spectroscopy under physiological conditions (pH 7.4). The results revealed that L2 and L2-Pt caused the fluorescence quenching of BSA through a static quenching procedure, and the quenching rate and quenching constants of L2-Pt on BSA are higher than those of L2 at 298, 304 and 310 K, respectively. The calculating of enthalpy change (ΔH) and the entropy change (ΔS) and gibbs free energy(ΔG) implied that the main interaction force of L2 with BSA was hydrophobic force(ΔH>0, ΔS>0), and the binding process was spontaneous(ΔG＜0). While the main interaction force of L2-Pt with BSA was hydrogen bonds and van der Waals forces (ΔH<0, ΔS<0), and the binding process also was spontaneous(ΔG＜0). The UV-Vis spectroscopy and synchronous fluorescence indicated that L2-Pt did not alter the microstructure of BSA.
Key words: platinum complex; bovine serum albumi; fluorescence spectrum; interaction; static quenching
引用本文：袁涛，覃姣兰，罗翠萍，等. 2-(2-氨基苯基)苯并咪唑铂(II)配合物的合成及其与BSA作用的光谱研究[J]. 化学试剂, 2023, 45(2): 62-68。
CYP1B1抑制剂研究进展
王志刚*，费荣杰
（南京化学试剂股份有限公司，江苏 南京 210047）
摘要：CYP1B1酶(Cytochrome P450 1B1, CYP1B1)是细胞色素P450酶(Cytochrome P450 enzyme, CYPs)的一个亚族，能参与多种内、外源性化合物的氧化/还原反应，在多种恶性肿瘤中高表达。CYP1B1酶逐渐成为是抗肿瘤药物设计研发的热门靶点，许多学者以CYP1B1酶为靶标蛋白设计的抑制剂表现出较好的活性和巨大的应用潜力，尤其是在克服肿瘤耐药性中具有重要意义。目前报道的CYP1B1抑制剂种类繁多，活性最佳的化合物是α-萘黄酮（ANF）。主要介绍了较为常见的几类CYP1B1抑制剂，简述了各类化合物的特点以及酶抑制效果，并对CYP1B1抑制剂的发展前景进行了展望。
关键字：CYP1B1酶；抑制剂；靶点；抗肿瘤；α-萘黄酮
中图分类号：R9 文献标识码：A 文章编号：0258-3283(2023)--
DOI: 10.13822/j.cnki.hxsj.2023.0035
Research Progress of CYP1B1 Inhibitors WANG Zhi-gang*, FEI Rong-jie (Nanjing Chemical Reagent Co. LTD, Nanjing 210047, China)
Abstract：Cytochrome P450 1B1 (CYP1B1) enzyme is a subfamily of Cytochrome P450 enzymes (CYPs), which can participate in the oxidation/reduction reaction of a variety of endogenous and exogenous compounds, and is highly expressed in a variety of malignant tumors. CYP1B1 enzyme has gradually becomed a popular target for the design and development of anti-tumor drugs. Many scholars have designed inhibitors targeting CYP1B1 enzyme, which show good activity and great application potential, especially in overcoming tumor drug resistance. A variety of CYP1B1 inhibitors have been reported, and the most active compound is α-naphthalene flavone (ANF). The review introduced several common classes of CYP1B1 inhibitors, briefly described the characteristics and enzyme inhibition effects of each compound, and look forward to the development prospects of CYP1B1 inhibitors.
Key words：CYP1B1 enzyme; inhibitor; a target point; antitumor; alpha-naphthalene flavone
引用本文：王志刚，费荣杰.CYP1B1抑制剂研究进展[J].化学试剂，2023,43（2）：69-74.
【功能材料】
赵孟雅，田璐，肖禹圣，王震寰，刘淑莹，赵幻希*，修洋*
（长春中医药大学 吉林省人参科学研究院，吉林 长春 130117）
摘要：多金属氧酸盐（Polyoxometalates, POMs）是由高价态的过渡金属离子通过氧连接而成的一类多金属氧簇化合物，因其丰富的元素组成、可调控的多样结构及氧化还原活性，在催化、材料和医药等领域拥有广泛的应用。POMs在极性溶剂中通常有良好的溶解度，这导致其不易从反应体系分离。制备复合型POMs，一方面可以提高POMs的比表面积和稳定性，进而提高催化活性；另一方面可以降低POMs在极性溶剂中的溶解度，有利于回收及重复利用。主要综述了近年来复合型POMs的合成、性质及应用的研究现状。
关键词：多金属氧酸盐；复合型材料；有机大环化合物；无机材料；催化剂；合成与应用
中图分类号：TQ426.91 文献标识码：A 文章编号：
DOI: 10.13822/j.cnki.hxsj.2022.0535
Synthesis and Applications of Composite Polyoxometalates ZHAO Meng-ya, TIAN Lu, XIAO Yu-sheng, WANG Zhen-huan, LIU Shu-ying, ZHAO Huan-xi*, XIU Yang*( Jilin Ginseng Academy, Changchun University of Chinese Medicine, Changchun 130117, China)
Abstract：Polyoxometalates (POMs) are metal oxide clusters formed by oxygen bonding of transition metals in high oxidation states, which have been applied to a wide range of fields: catalysis, materials and medicine due to its rich constituent elements, tunable architectures and redox properties. The high solubility of POMs in polar solvents give rise to the difficultly in separation from the reaction system. By preparation of composite POMs, on the one hand, the surface areas and stability can be increased in comparison with its parent POMs to further improve the catalytic activity. On the other hand, it can reduce the solubility of POMs in polar solvents, which is convenient for recycling and reusing. The different synthetic methodologies, properties, and applications of composite POMs in recent years were reviewed.
Key words：polyoxometalates; composite materials; organic macrocyclic compounds; inorganic materials; catalysts; synthesis and applications
引用本文: 赵孟雅，田璐，肖禹圣，等. 复合型多金属氧酸盐的合成与应用[J]. 化学试剂, 2023, 45(2):75-82。
废弃烟滤嘴制备醋酸纤维素微球及其对Pb(II)的吸附性能
陈燕敏*,刘冰，赵文伯，卢鑫，邵冰琪
（郑州师范学院 化学化工学院，河南 郑州 450044）
摘要：采用双重乳液溶剂挥发法与气体发泡技术相结合的方法将从废弃卷烟滤嘴中再生得到的醋酸纤维素进行改性，制备出醋酸纤维素多孔微球。通过扫描电镜、氮吸附和压汞法考察了内水相发泡剂用量和搅拌速度对微球形貌、比表面积和孔结构的影响，并进一步研究了其对重金属Pb2+离子的吸附性能。结果表明：随发泡剂用量增大，微球粒径逐渐变大，比表面积先增加后稍有下降，由闭孔转化为贯通孔；随搅拌速度加大，微球粒径逐渐减小，比表面积呈增大趋势，高速搅拌下具有更多的贯通孔结构。静态吸附结果显示，所制备醋酸纤维素多孔微球对Pb2+离子吸附量可达57.6 mg/g，远远优于未采用发泡剂技术所得微球的吸附性能。吸附动力学以及吸附等温实验表明该醋酸纤维素微球对Pb2+离子的吸附符合准二级动力学模型和Freundlich吸附等温模型。
关键词：废弃卷烟滤嘴；回收再生；醋酸纤维素微球；吸附；Pb2+
中图分类号：TQ352.9 文献标识码：A 文章编号：0258-3283(2023)
DOI: 10.13822/j.cnki.hxsj.2022.0671
Preparation of Cellulose Acetate Microspheres from Waste Cigarette Filters and Its Adsorption Properties for Pb2+ CHEN Yan-min*, LIU Bing, ZHAO Wen-bo, LU Xin, SHAO Bing-qi (College of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China)
Abstract: The cellulose acetate regenerated from waste cigarette filters was modified by the combination of dual emulsion solvent evaporation and gas foaming technology to prepare the cellulose acetate porous microspheres. The effects of the amount of foaming agent and stirring speed on the morphology, surface area and pore structure of the microsphere were investigated by scanning electron microscope (SEM), N2 adsorption and mercury intrusion porosimetry (MIP). The results showed that the diameter of microsphere gradually increased, the surface area increased at first and then decreased slightly and closed pores transformed to through pores with the adding of foaming agent. With the increment of stirring speed, the diameter of microsphere gradually decreased, and the surface area increased, leading to more through-holes structure appeared under high-speed stirring. The results of static adsorption revealed that the Pb2+ adsorption capacity of the cellulose acetate microspheres was up to 57.6 mg/g, which was much better than that of the microspheres without blowing technology. Adsorption kinetics and adsorption isotherm experiments showed that the Pb2+ adsorption of cellulose acetate microsphere was compliant with quasi-second-order kinetic model and Freundlich adsorption isothermal model.
Key words: waste cigarette filters; recycling; cellulose acetate microsphere; adsorption; Pb2+
引用本文：陈燕敏, 刘冰, 赵文伯, 等. 废弃烟滤嘴制备醋酸纤维素微球及其对Pb(II)的吸附性能[J]. 化学试剂, 2023,45（2）：83-89.
【分离提取技术】
响应面法优化酶法制备薏苡仁寡糖工艺研究
郑舒怡1,3,4，左佳昕1,3,4，戴鑫1,3,4，高淑娟1,3,4，张怡1,2,3,4，卢旭*1,2,3,4
(1.福建农林大学 食品科学学院，福建 福州，350002；
2.福建省特种淀粉品质科学与加工技术重点实验室，福建 福州，350002；
3.中国-爱尔兰国际合作食品物质学与结构设计研究中心，福建 福州，350002；
4.农业农村部亚热带特色果蔬菌加工重点实验室（部省共建），福建 福州，350002)
摘要：以薏苡仁为原料，选取酶解温度、液料比、α-淀粉酶添加量以及酶解时间4个因素进行单因素试验，利用响应面法建立数学模型，根据所得模型分析4个因素对寡糖得率的影响，最后对提取工艺进行优化。结果表明最佳工艺条件为：料液比1 ：16.41（g/mL）、酶添加量0.91 g、酶解时间111.49 min、酶解温度45.46 ℃，其中对薏苡仁寡糖得率影响最大的因素条件为酶解温度。在该条件下，薏苡仁寡糖得率为33.01%，与模型预测值33.19%接近，该工艺条件切实可行，可用于预测薏苡仁寡糖的提取。
关键词：薏苡仁；寡糖；酶解；响应面；提取过程
中图分类号：TS201.4 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0696
Optimization of Enzymatic Preparation of Coix Lacryma Oligosaccharides by Response Surface Methodology ZHENG Shu-yi1,3,4, ZUO Jia-xin1,3,4, DAI Xin1,3,4, GAO Shu-juan1,3,4, ZHANG Yi1,2,3,4, LU Xu*1,2,3,4 (1. College of Food Science，Fujian Agriculture and Forestry University, Fuzhou 350002; 2. Fujian Provincial Key Laboratory of Quality Science and Processing Technology in Special Starch, Fuzhou 350002, China; 3. China-Ireland International Cooperation Centre for Food Material Science and Structure Design,, Fuzhou 350002, China; 4.Key Laboratory of Subtropical Characteristic Fruits, Vegetables and Edible Fungi Processing (Co-construction by Ministry and Province), Ministry of Agriculture and Rural Affairs，Fuzhou 350002, China)
Abstract: Firstly, the four factors of enzymatic digestion temperature, liquid to material ratio, α-amylase addition and enzymatic digestion time were selected as the raw material of coix lacryma for the single-factor test. Then using the response surface method to establish a mathematical model. The resulting model was used to analyse the effect of four factors on the oligosaccharide yield, and finally, the extraction process was optimised. According to the experiment results, the optimum process conditions were that the ratio of liquid and material was 1 ：16.41（g/mL）, enzyme addition was 0.91 g, enzymatic digestion time was 111.49 min, and enzymatic digestion temperature was 45.46 ℃. The enzymatic digestion temperature was the most influential factor on the yield of coix lacryma oligosaccharides. Under these conditions, the yield of coix lacryma oligosaccharide was 33.01%, which was close to the model prediction of 33.19%. The process conditions were practicable and could be used to predict the extraction of coix lacryma oligosaccharide.
Key words：Coix lacryma; oligosaccharides; enzymatic digestion; response surface; extraction process
引用本文：郑舒怡，左佳昕，戴鑫，等. 响应面法优化酶法制备薏苡仁寡糖工艺研究[J]. 化学试剂，2023，45（2）：90-97.
红毛藻不同乙醇浓度提取物的生物活性及其成分分析
常高萍1，林巧燕1，张敏1，郭佳瑄1，李志朋*1,2,3,4，杜希萍1,2,3,4，姜泽东1,2,3,4
（1. 集美大学 海洋食品与生物工程学院，福建 厦门 361021；2. 福建省食品微生物与酶工程重点实验室，福建 厦门 361021；3. 厦门市食品与生物工程技术研究中心，福建 厦门 361021；4. 厦门南方海洋研究中心海藻资源化利用与深加工重点实验室，福建 厦门 361021）
摘要：为了探究红毛藻乙醇提取物活性成分及其功能活性，使用不同浓度乙醇溶液提取红毛藻，并测定不同浓度乙醇溶液提取物中的总多酚、总生物碱、总黄酮含量。通过研究胰脂肪酶、酪氨酸酶、乙酰胆碱酯酶抑制活性和DPPH自由基清除能力来评价不同浓度乙醇溶液提取红毛藻的活性差异。通过LC-MS/MS技术完成红毛藻乙醇提取物中的多酚鉴定。结果表明，红毛藻不同乙醇浓度提取物均具有DPPH清除能力以及酪氨酸酶、胰脂肪酶、乙酰胆碱酯酶抑制活性，乙醇浓度不同，其提取物生物活性不同，总多酚、总黄酮、总生物碱含量不同；其中100%乙醇浓度提取物总多酚、总黄酮和总生物碱含量最高，具有较强的DPPH清除能力和酪氨酸酶抑制活性。同时结果还表明，总多酚和总黄酮含量与酪氨酸酶抑制活性和DPPH清除能力均具有极显著相关性。LC-MS/MS结果显示红毛藻100%乙醇提取物中含有37种多酚类化合物。
关键词：红毛藻；生物活性；成分分析；相关性分析；LC-MS/MS
中图分类号：TS201.1 文献标志码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0718
Bioactivity and Component Analysis of Different Ethanol Concentration Extracts from Bangia Fusco-purpurea CHANG Gao-ping1, LIN Qiao-yan1, ZHANG Min1, GUO Jia-huan1, LI Zhi-peng*1,2,3,4, DU Xi-ping1,2,3,4, JIANG Ze-dong1,2,3,4 (1. College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China; 2. Fujian Provincial Key Laboratory of Food Microbiology and Enzyme Engineering, Xiamen 361021, China; 3. Research Center of Food Biotechnology of Xiamen City, Xiamen 361021, China; 4. Key Laboratory of Systemic Utilization and In-depth Processing of Economic Seaweed of Southern Ocean Technology Center of Xiamen, Xiamen 361021, China)
Abstract: For exploring the active constituents and functions of ethanol extracts from Bangia fusco-purpurea, the contents of total polyphenols, alkaloids and flavonoids were determined. The inhibitory effects of pancreatic lipase, tyrosinase and acetylcholinesterase and DPPH free radical scavenging were evaluated. The identification of polyphenols in ethanolic extracts of B. fusco-purpurea was completed by LC-MS/MS. The results showed that different ethanol concentration extracts from B. fusco-purpurea had different DPPH scavenging ability, tyrosinase, pancreatic lipase and acetylcholinesterase inhibitory activity, and different contents of total polyphenols, flavonoids, alkaloids. 100% ethanol extract from B. fusco-purpurea had the highest contents of total polyphenols, flavonoids, alkaloids, and stronger DPPH scavenging ability and tyrosinase inhibitory activity. Correlation analysis showed that the contents of total polyphenols and flavonoids were significantly correlated with tyrosinase inhibitory activity and DPPH scavenging ability. LC-MS/MS results revealed 37 polyphenolic compounds in 100% ethanolic extract from B. fusco-purpurea.
Key words: Bangia fusco-purpurea; biological activities; component analysis; correlation analysis; LC-MS/MS
引用本文：常高萍，林巧燕，张敏，等. 红毛藻不同乙醇浓度提取物的生物活性及其成分分析[J]. 化学试剂, 2023, 45(2): 98-105。
相关性研究
程婉婷a，陈世钰b，贤凤a，胡坤b，高静*b
（广东药科大学 a.公共卫生学院，广东 广州 510000；b.食品科学学院，广东 中山 528400）
摘要：制备7种酸性低共熔溶剂（DES），在不同温度下系统测定低共熔溶剂的理化特性，评估了虾青素的溶解度，并与有机溶剂和离子液体进行比较，深入探讨虾青素溶解度与低共熔溶剂理化性质之间的关联性。结果表明，7种酸性低共熔溶剂具有低黏度和良好的热稳定性；虾青素在7种低共熔溶剂中的溶解效果均优于乙醇与离子液体三丁基辛基氯化膦，溶解能力最强的是DL-薄荷醇:乙酸，可达（405.94 ± 12.90） mg/100g；低共熔溶剂的密度、黏度和偶极性/极化率3个性质与虾青素溶解能力密切相关，相关系数分别为0.99、-0.85和0.83，这为选择和设计提取天然类胡萝卜素的溶剂及其应用提供了理论指导。
关键词：低共熔溶剂；理化性质；虾青素；溶解度
中图分类号：TQ413 文献编识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0704
Physicochemical Properties of Acidic Deep Eutectic Solvents and the Correlation with Astaxanthin Solubility CHENG Wan-tinga, CHEN Shi-yub, XIAN Fenga, HU Kunb, GAO Jing*b (a. School of Public Health, Guangzhou 510000, China; b. School of Food Science, Guangdong Pharmaceutical University, Zhongshan, 528400, China)
Abstract: 7 Acidic deep eutectic solvents (DES) were prepared, and the effects of temperature on the physicochemical properties were explored. In addition, solubility of astaxanthin in different DES was measured and compared with organic solvent and ionic liquid (IL). Moreover, the correlation coefficients of the physicochemical properties and astaxanthin solubility were analyzed. The results showed that the acidic DES presented low viscosity and favourable thermal stability. The solubility of astaxanthin in all the DES was higher than that in ethanol and IL (tributyl(octyl)phosphonium chloride). Besides, DL-menthol: acetic acid (MAA) showed the highest astaxanthin solubility of (405.94 ± 12.90) mg/100g. Furthermore, the correlation analysis showed that the astaxanthin solubility was significantly correlated with density, viscosity and dipolarity of DES, whose related coefficients are 0.99, -0.85 and 0.83 respectively. The study provides theoretical guidance for the pre-selection and design of suitable solvents for the extraction of carotenoids and their applications.
Key words: deep eutectic solvent; physicochemical properties; astaxanthin; solubility
引用本文：程婉婷, 陈世钰, 贤凤, 等. 酸性低共熔溶剂的理化特性及其与虾青素溶解度的相关性研究[J]. 化学试剂, 2023, 45（2）：106-113.
响应面法优化毛大丁草总香豆素提取工艺及其抗氧化作用研究
高奇1,2，李齐激1,2，杨柳2，杨娟1,2，孙超*1,2
（1. 贵州医科大学 药学院，贵州 贵阳 550025；2. 贵州省中国科学院天然产物化学重点实验室，贵州 贵阳 550014）
摘要：以毛大丁草为研究对象，选择提取温度、提取溶剂、料液比和提取时间进行单因素实验，在单因素实验基础上，采用Box-Behnken响应面法优化其总香豆素提取工艺，并测定不同产地毛大丁草总香豆素提取率及评价其体外抗氧化活性。结果表明，其最佳提取工艺为提取温度85 ℃，乙醇体积分数60%，料液比 1:40（g/mL），提取时间60 min。不同产地中清除率最高的为广西百色市样品，IC50为0.36 mg/mL；最低的是贵州黔南州样品，IC50为121.43 mg/mL。不同产地兰香草总黄酮具有一定的总抗氧化能力，能够有效地清除DPPH自由基，效果弱于同浓度条件下VC。经验证该工艺合理、简便，总香豆素提取率可达1.66%。
关键词：毛大丁草；总香豆素；提取工艺；响应面法；抗氧化活性
中图分类号：R932 文献标识码：A 文章编号：0258-3283（2022）--
DOI: 10.13822/j.cnki.hxsj.2022.0700
Optimization of Extraction Process of Total Coumarins from Piloselloides Hirsuta by Response Surface Methodology and iIts Antioxidant Effect GAO Qi 1,2, LI Qi-ji 1,2, YANG Liu2, YANG Juan 1,2, SUN Chao1,2*(1. College of Pharmacy, Guizhou Medical University, Guiyang 550025; 2. The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guiyang 550014, China.)
Abstract: Single factor experiments were carried out by choosing extraction solvent, solid-liquid ratio, extraction time and extraction temperature from Piloselloides hirsuta. Based on the results of single factor experiments, the Box-Behnken response surface methodology was used to optimize the extraction process of total coumarins, and the contents of total coumarins in Piloselloides hirsuta from different areas was determined and their antioxidant activities in vitro were compared and evaluated. The optimal reflux extraction process were as follows: extraction temperature 85 ℃, ethanol concentration 60%,solid-liquid ratio 1∶40 g/mLand extraction time 60 min. The content of total coumarins of Piloselloides hirsuta from ten different areas are varied.Among them,the highest content of total flavonoids is from Baise, Guangxi, with IC50 of 0.36 mg/mL; the lowest content is from Qiannan Prefecture, Guizhou, with IC50 of 121.43 mg/mL. The total coumarins of Piloselloides hirsuta fromd ifferent areas have a certain total antioxidant capacity, and they can scavenge DPPH radical effectively, which are all weaker than the same concentration of vitamin C. It has been proved that the process is reasonable and simple, and the extraction rate of total coumarins can reach 1.66%.
Key words: sargassum pilosum; total coumarins; extraction process; response surface methodology; antioxidant activity
引用本文：高奇，李齐激，杨柳，等. 响应面法优化毛大丁草总香豆素提取工艺及其抗氧化作用研究[J]. 化学试剂, 2023, 45( 2): 114-120。
【化学品与环境】
3-甲醛肟基苯甲酸乙酯的合成及其对部分重金属离子的荧光选择识别
董艳芹，刘欣宇，曾展鹏，彭佩，王勇*
(荆楚理工学院 化工与药学院 药物合成与优化湖北省重点实验室，湖北 荆门 448000)
摘要：基于肟类化合物对重金属离子具有很好的配位能力，是一类制备荧光探针的优良配体。将3-溴苯甲酸与二氯亚砜在乙醇中直接反应制得为制得中间体3-溴苯甲酸乙酯（L2）。接着将中间体L2与氰化亚铜直接反应得到中间体3-氰基苯甲酸乙酯（L3），最后将中间体L3与盐酸羟胺在碳酸钠存在制得标题化合物L4。对化合物L2 ~ L4进行核磁共振氢谱、碳谱和红外光谱等结构表征。利用电子吸收光谱和荧光光谱研究了常见重金属离子（Cu(II)、Fe(III)、Pb(II)、Co(II)、Cr(III)、Ni(II)、Fe(II)、Mn(II)、Zn(II)和Cd(II)）对目标化合物L4的选择性，研究表明目标化合物对Cu(II)、Fe(III)和Pb(II)离子表现优良的选择作用。随着金属离子Cu(II)、Fe(III)和Pb(II)的加入，目标化合物L4的荧光强度均逐渐减弱至基本完全猝灭，而对其他重金属离子没有选择识别作用或选择识别作用较弱。
关键词：肟；重金属离子；荧光光谱；电子吸收光谱；设计合成
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0576
Synthesis of 3-(hydroxyimino-methyl)-benzoic Acid Ester and its Fluorescence Recognition of Selected Heavy Metal Ions DONG Yan-qin, LIU Xin-yu, ZENG Zhan-peng, PENG Pei, WANG Yong* (Key Laboratory of Drug Synthesis and Optimization, College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen, 448000, China)
Abstract：Oxime-based compounds have good coordination ability to heavy metal ions, and which are excellent ligands for the preparation of fluorescent probes. 3-Bromobenzoic acid ethyl ester (L2) was obtained by reaction of 3-bromobenzoic acid (L1) with thionyl chloride in ethanol. 4-Cyano-2-methyl-benzoic acid methyl ester (L3) was synthesized by reaction of L2 with cuprous cyanide. And finally reaction of ethyl 3-cyanobenzoate with hydroxylamine hydrochloride in the presence of sodium carbonate affords ethyl formaloximinobenzoate (L4). The structures of L2 ~ L4 were characterized by 1HNMR, 13CNMR and IR. The electron absorption spectroscopy and fluorescence spectroscopy were used to investigate the interaction of selected heavy metal ions (Cu(II), Fe(III), Pb(II), Co(II), Cr(III), Ni(II), Fe(II), Mn(II), Zn(II) and Cd(II)) with L4. The study showed that L4 possessed excellent selectivity for Cu(II), Fe(III) and Pb(II) ions. With the addition of metal ions Cu(II), Fe(III) and Pb(II), the fluorescence intensity of L4 gradually weakened, and even almost to be quenched completely, while it had no selective recognition effect or weak selective recognition effect on other heavy metal ions.
Key words：oximes；heavy metal ions；fluorescence spectroscopy；electron absorption spectroscopy；design and synthesis
引用本文：董艳芹，刘欣宇，曾展鹏，等. 3-甲醛肟基苯甲酸乙酯的合成及其对部分重金属离子的荧光选择识别[J].化学试剂，2023,45（2）：121-127
ZnCuNi-LDHs的制备及其对MO吸附性能研究
李阳1，王泽华1，田慧媛1，李萍1，崔节虎*1,2
（1.郑州航空工业管理学院 材料学院，河南 郑州 450000；2.郑州市环境功能材料重点实验室，河南 郑州 450000)
摘要：以硝酸锌、硝酸铜和硝酸镍为原料，三乙醇胺为碱源，采用水热合成法制备出3种ZnCuNi- LDHs复合纳米材料，并用于染料废水甲基橙中阴性离子的吸附研究。结果表明，ZnCuNi-LDHs吸附甲基橙符合准二级动力学模型，吸附反应为化学吸附，自发放热反应。考察各种条件下的吸附能力，在25 ℃、初始pH的条件下，向20 mL（20 mg/L）甲基橙溶液中投加25 mg ZnCuNi-LDHs，对甲基橙的去除率分别可达98.5%、94.7%、92.4%；对MO最大吸附量分别为1163、1230、1712 mg/g；经过3次循环利用后，Zn-Cu-Ni-LDHs 对甲基橙的吸附率仍分别可达71.5%、61.2%、50.6%。
关键词：Zn-Cu-Ni-LDH；甲基橙；吸附；水处理技术；循环利用
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0618
Study on the preparation of ZnCuNi-LDHs and their adsorption properties for MO LI Yang1, WANG Ze-hua1, TIAN Hui-yuan1, LI Ping1, CUI Jie-hu*1,2 (1. The College of Materials Science and Engineering, Zhengzhou University of Aeronautical, Zhengzhou 450000, China; 2 Key Laboratory of Environment Functional Materials, Zhengzhou University of Aeronautical, Zhengzhou 450000, China)
Abstract：Using zinc nitrate, copper nitrate and nickel nitrate as raw materials, and triethanolamine as the base source, three ZnCuNi-LDHs composite nanomaterials were prepared by hydrothermal synthesis method for the adsorption of negative ions of methyl oranges existed in dye wastewater. The results showed that ZnCuNi-LDHs adsorb methyl orange in line with the quasi-secondary kinetic model, and the adsorption reaction was chemical adsorption and self-release thermal reaction. The adsorption capacity under various conditions was investigated, and the removal rate of methyl orange was 98.5%, 94.7% and 92.4%, respectively, by adding 20 mL(20 mg/L)methyl orange solution under the condition of 25 °C and initial pH. The maximum adsorption of MO was 1163, 1230, and 1712 mg/g, respectively. After three cycles, the adsorption rate of ZnCuNi-LDHs on methyl oranges can still reach 71.5%, 61.2% and 50.6%, respectively.
Key words：Zn-Cu-Ni-LDH; methyl orange; adsorption; water treatment technology; recycling
引用本文：李阳，王泽华，田慧媛，等. ZnCuNi-LDHs的制备及其对MO吸附性能研究[J].2023，45（2）：128-133.
MnOx@Fe3O4复合材料制备及其对苯酚处理性能研究
高卫民*，程寒飞，朱巧红，冉景
（中冶生态环保集团有限公司，北京 10020）
摘要：首先通过采用两步法设计制备磁性纳米复合材料MnOx@Fe3O4，然后测量其粒度的分布状态，再通过扫描电镜（SEM）、X-射线衍射（XDR）和红外光谱（IR）3种方法表示其结构形态；初步研究了磁性纳米MnOx@Fe3O4复合物分子结构与组成，深入分析了该磁性纳米复合材料的添加量和改变苯酚的初始浓度对该复合材料活化PMS分解苯酚性能的影响，并研究了纳米MnOx@Fe3O4复合材料循环使用的效果。结果表明，磁性纳米复合材料MnOx@Fe3O4是α-MnO2表面负载四氧化铁（Fe3O4）的复合材料，平均粒径为247.3 nm，磁分离性好；纳米MnOx@Fe3O4复合材料有较好的活化PMS分解苯酚的效果，在处理初始浓度为10 mg/L的酚类废水之后，添加80 mg/L该复合材料，用时180 min，效果明显，去除率达到100%；随着苯酚的浓度逐渐提高，同一添加量的MnOx@Fe3O4活化PMS分解去除效果会下降；MnOx@Fe3O4活化PMS循环使用效果较好，对10 mg/L的苯酚废水，反复使用6次，还有90%以上的去除率。
关键词：磁性；MnOx@Fe3O4复合材料；含酚废水；高级氧化
中文分类号：X506 文章标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0374
Preparation of Magnetic Nano-MnOx@Fe3O4 Composite and Its Treatment Performance of Phenol GAO Wei-min*, CHENG Han-fei, ZHU Qiao-hong, RAN Jing (MCC Ecological Environmental Protection Group Co., Ltd, Beijing 100020, China)
Abstract: Nano-MnOx@Fe3O4 composite was designed and prepared by two-step method, and the particle size distribution was measured. The structural morphology was analyzed by scanning electron microscope (SEM), X-ray diffraction (XDR) and infrared spectrum (IR) three methods. The structural composition of nano-MnOx@Fe3O4 composite was preliminarily discussed. The effects of the addition amount of nano-MnOx@Fe3O4 composites and different initial concentrations of phenol on the performance of nano-MnOx@Fe3O4-activated PMS to decompose phenol were investigated, and the effect of recycling nano-MnOx@Fe3O4 composites was also studied. The results showed that the nano-MnOx@Fe3O4 composite materialwas a composite material with iron tetroxide (Fe3O4) loaded on the surface of α-MnO2, the average particle size was 247.3 nm, and the magnetic separation is excellent; the nano-MnOx@Fe3O4 composite material had a good effect of activating PMS to decompose phenol. The addition amount of 80 mg/L can reach 100% removal rate of phenol waste with a concentration of 10 mg/L in 180 min. When the initial concentration of phenol increases, the decomposition effect of the same amount of nano-MnOx@Fe3O4 activated PMS will decrease. The recycling effect of nano-MnOx@Fe3O4 activated PMS was better, which can be reused 6 times to deal with the phenol waste with an initial concentration of 10 mg/L. Over 90% removal rate was still obtained.
Key words: magnetism; MnOx@Fe3O4 composite; phenol-containing wastewater; advanced oxidation
引用本文：高卫民, 程寒飞, 朱巧红, 等. MnOx@Fe3O4复合材料制备及其对苯酚处理性能研究[J]. 化学试剂, 2023, 45（2）：134-140.
【分析与测试】
超高效液相色谱串联质谱法测定葡萄酒中酚酸和酚醛类化合物
马燕玲1,2，王一名1，初坤1，陈晨1，吴帅*1
（1.烟台市食品药品检验检测中心，山东 烟台 264000；2.青岛市农业科学研究院，山东 青岛 266100）
摘要：建立了超高效液相色谱-三重四极杆串联质谱法检测葡萄酒中18种酚酸和酚醛类物质的方法。将葡萄酒经0.22 μm PTFE滤膜过滤后进样，选用ACQUITY UPLC HSS T3色谱柱（2.1 mm × 100 mm，1.8 μm），以0.1%（V/V）甲酸乙腈溶液-0.1%（V/V）甲酸水溶液为流动相，采用梯度洗脱方式，对酚类物质进行分离。选择电喷雾离子源（ESI），采用多反应监测（MRM）的模式，优化质谱参数。实验结果表明，18种酚酸和酚醛类物质在各自的质量浓度范围内均呈良好的线性关系，检出限在0.2～4 μg/L之间，定量限在0.8～10 μg/L之间，平均回收率为75.0%～98.8%，精密度为1.68%～6.19%。利用上述方法对葡萄酒样品进行分析，结果表明，所有葡萄酒中均含有没食子酸、咖啡酰酒石酸、对羟基苯甲酸、丁香酸、香草酸等酚类物质，未检出原儿茶酸、鞣花酸、水杨酸和肉桂酸等，部分酒样中检出芥子酸。该方法能够满足葡萄酒酚酸和酚醛类物质检测的定量和定性要求。
关键词：超高效液相色谱-串联质谱法；葡萄酒；酚酸类；酚醛类；过滤
中图分类号：O652.63 文献标志码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0757
Determination of Phenolic Acids and Phenol Aldehyde Compounds in Wine by Ultra Performance Liquid Chromatography Tandem Mass Spectrometry MA Yan-ling1,2, WANG Yi-ming1, CHU Kun1, CHEN Chen1, WU Shuai*1 (1. Yantai Testing Center for Food and Drug, Yantai 264000, China; 2. Qingdao Academy of Agricultural Sciences, Qingdao 266100, China)
Abstract: A method for the separation of 18 kinds of phenolic acid and phenol aldehyde compounds in wine was developed by ultra performance liquid chromatography tandem mass spectrometry. Wines filtered after 0.22 μm membrane were analyzed using ACQUITY UPLC HSS T3 (2.1 mm×100 mm, 1.8 μm). The composition were isolated by the mobile phase of 0.1%（V/V）formic acid acetonitrile and 0.1%（V/V）formic acid water using gradient elution. The qualitative and quantitative analyses were operated under multiple reaction monitoring (MRM) mode using electrospray ion source (ESI) mode. The test results showed that the compounds to be tested presented a good linear relationship in respective mass concentration ranges. The limits of detection (LODs) were between 0.2～4 μg/L and the limits of quantification (LOQs) were 0.8～10 μg/L. The average recovery was in the range of 75.0%～98.8% with the precision from 1.68% to 6.19%. The above methods were used to analyze the wine samples. The results showed that gallic acid, caftaric acid, p-hydroxybenzoic acid, syringic acid, vanillic acid and other phenolic substances were found in all wines. Ellagic acid, 3,4-dihydroxybenzoic acid, salicylic acid and cinnamic acid were not detected in wine. Sinapic acid was detected in a few wine samples. This method was proved to be accurate for the analysis of phenolic acid and phenol aldehyde compounds in wine.
Key words: UPLC-MS/MS; wine; phenolic acid; phenol aldehyde; filter
引用本文：马燕玲，王一名，初坤，等. 超高效液相色谱串联质谱法测定葡萄酒中酚酸和酚醛类化合物[J]. 化学试剂, 2023, 45( 2): 141-147。
一测多评法测定黑果小檗果实中5种花色苷含量
陈玲1，包海燕1，阳莹1，李敏1，李慧敏1，康莹莹1，李建光*1,2
（1. 新疆医科大学 药学院，新疆 乌鲁木齐 830011；2. 新疆科技学院 医学院，新疆 库尔勒 841000）
摘要：建立高效液相色谱一测多评法（HPLC-QAMS）测定黑果小檗果实中5种花色苷的含量。采用Welch TopsilTM C18（250 mm × 4.6 mm，5 μm）色谱柱；流动相为甲醇-2.5%甲酸水溶液，梯度洗脱；检测波长为520 nm；流速为0.8 mL/ min；柱温为35 oC；进样量为10 μL。以矢车菊素-3-O葡萄糖苷为内参物，建立飞燕草素-3-O-葡萄糖苷、矮牵牛素-3-O-葡萄糖苷、芍药素-3-O-葡萄糖苷以及锦葵素-3-O-葡萄糖苷的相对校正因子，并计算各成分含量，同时与外标法测定结果进行对比。5种花色苷分别在各自浓度范围内与峰面积的线性关系良好（0.9994 ≤ R2 ≤0.9996）；平均加样回收率为99.44% ~ 101.72%，RSD为1.32% ~ 2.59%；6批不同产地的黑果小檗采用QAMS法与外标法所测含量无显著性差异（P ＞ 0.05）。该方法可用于黑果小檗果实中5种花色苷的含量测定。
关键词：黑果小檗；花色苷；一测多评法；相对校正因子；含量测定
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0666
Determination of Five Anthocyanins in Berheris Heteropoda Schrenk Fruit by QAMS Method CHEN Ling1, BAO Hai-yan1, YANG Ying1, LI Min1, LI Hui-min1, KANG Ying-ying1, LI Jan-guang*1,2 (1. College of Pharmacy, Xinjiang Medical University, Urumqi 830011, China; 2. School of Medicine, Xinjiang University of Science and Technogy, Korla 841000, China)
Abstract: To establish a high performance liquid chromatography-quantitative analysis of multi-component by single marker (HPLC-QAMS) method for determination of five anthocyanins in Berberis heteropoda Schrenk fruit. Welch TopsilTM C18 (250 mm × 4.6 mm, 5 μm) was used as the column with methanol-2.5% formic acid water as the mobile phase by gradient elution. The detection wavelength was set at 520 nm, the flow rate was 0.8 mL/ min, the column temperature was 35 oC and the injection volume was 10 μL. The relative correction factors of delphinidin-3-O-glucoside, petunidin-3-O-glucoside, peonidin-3-O-glucoside and malvidin-3-O-glucoside were established with cyanidin-3-O-glucoside as internal reference. The contents of each component were calculated and compared with the results of external standard method. Five anthocyanins show good linear relationships within their own ranges（0.9994 ≤ R2 ≤ 0.9996）；whose average recoveries are 99.44% ~ 101.72% with the RSD of 1.32% ~ 2.59%. There was no significant difference between QAMS method and external standard method in the results of 6 batches of Berberis heteropoda Schrenk fruits from different producing areas (P＞0.05). The established method can be used for the determination of five anthocyanins in Berberis heteropoda Schrenk fruits.
Key words: berheris heteropoda schrenk; anthocyanin; QAMS; relative correction factor; content determination
引用本文：陈玲, 包海燕, 阳莹, 等. 一测多评法测定黑果小檗果实中5种花色苷含量[J]. 化学试剂, 2023,45（2）：148-154.
【标准物质与标准品】
纳摩尔级一氧化氮标准气体的制备技术研究
高冰1,2，王帅斌1,2，杨静1,2，封跃鹏1,2，倪才倩*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：采用称量法经四级稀释制备纳摩尔级（50 nmol/mol）氮气中一氧化氮标准气体，采用化学发光法分析氮气中一氧化氮标准气体，考察了制备重复性、气瓶内壁吸附解吸作用、瓶内均匀性和时间稳定性，开展了比对分析研究。结果表明，抛光气瓶可满足纳摩尔级一氧化氮标准气体的制备需求，一氧化氮在抛光气瓶内壁的吸附解吸作用可以忽略不计。浓度水平为50 nmol/mol的氮气中一氧化氮标准气体具有良好的制备重复性、瓶内均匀性和时间稳定性，且与具有国家标准样品编号的稀释为同一浓度水平的一氧化氮标准气体具有较好的量值一致性。该标准气体可为环境空气氮氧化物监测提供可靠的技术支持。
关键词：纳摩尔级；一氧化氮；标准气体；均匀性；稳定性；比对分析
中图分类号：X830.5 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2022.0662
Preparation of Nanomolar Nitric Oxide Gas Standard GAO Bing1,2, WANG Shuai-bin1,2, YANG Jing1,2, FENG Yue-peng1,2, NI Cai-qian*1,2 (1.Institute for Environmental Reference Materials Ministry of Environmental Protection, Beijing 100029, China; 2.State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Beijing 100029, China)
Abstract: The nanomolar nitric oxide gas standard material with concentration of 50 nmol/mol in nitrogen was prepared using a four-step weighing method. The gas standard material was analyzed by using Chemiluminescence method, and the preparation repeatability, adsorption and desorption effect of the inner wall, in-bottle uniformity and time stability of nitric oxide gas standard material were investigated. In addition, comparison analysis was also conducted. The related results demonstrated that the polished cylinders can meet the preparation needs of standard nanomolar nitric oxide gas. The adsorption and desorption effect of nitric oxide on the inner walls of polished cylinders can be ignored. The nitric oxide gas standard material (50 nmol/mol) in nitrogen had good preparation repeatability, in-bottle uniformity and time stability. Moreover, it had good value consistency with the standard nitric oxide gas along with the national standard sample number diluted to the same concentration level. The gas standard can supply the standards support for the nitrogen oxides determination in ambient air.
Key words: nanomolar; nitric oxide; gas standard; homogeneity; stability; comparison analysis
引用本文：高冰，王帅斌，杨静，等. 纳摩尔级一氧化氮标准气体的制备技术研究[J]. 化学试剂, 2023, 45(2 ): 155-160。
【合成与工艺技术】
高纯二水合连四硫酸钠的制备及其表征
刘红梅*1,2，谷芳芳1,2，王保金1,2，李炳华1,2，杜荣光1,2，陈勉彬1,2
(1.广州化学试剂厂，广东 广州 510288；2.广东广试试剂科技有限公司，广东 肇庆 526238)
摘要：在低温条件下，硫代硫酸钠与固体碘反应，经重结晶制得高纯二水合连四硫酸钠，并用XRD和IR对其结构进行了表征。结果表明，最佳制备条件为：氧化剂碘要比计量比稍过量一点，反应温度在10 ℃以下，至少需要重结晶1次；XRD图表明，该工艺制备的产品XRD图与标准图谱基本一致；IR图谱表明，连四硫酸钠中所含杂质硫代硫酸盐对红外图谱有较大的影响，硫代硫酸盐含量越低，在1238 ~ 1090 cm-1区间内的吸收峰越少，曲线越平滑。
关键词：连四硫酸钠；高纯度；制备；表征
中图分类号：TQ125.1 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0472
Preparation and Characterization of High-purity Sodium Tetrathionate Dihydrate LIU Hong-mei*1,2，GU Fang-fang1,2，WANG Bao-jin1,2，LI Bing-hua1,2，DU Rong-guang1,2，CHEN Mian-bin1,2 (1. Guangzhou Chemical Reagent Factory, Guangzhou 510288, China; 2. Guangdong Guangshi Reagent Technology Co., Ltd，Zhaoqing 526238, China)
Abstract：The high purity of sodium tetrathionate dihydrate was prepared by the reaction between iodine and sodium thiosulphate at low temperature. It was recrystallized from a cool aqueous solution by the addition of ethanol. Its structure was characterized by XRD and IR. Based on the experiment results, the best preparation method is that the addition of oxidant iodine was slightly excessive than the stoichiometric ratio, the reaction temperature was below 10 ℃, and the recrystallization was required at least once. The XRD pattern showed that the XRD diagram of the products prepared by this process was basically consistent with the standard diagram of sodium tetrathionate dehydrate. The IR spectra showed that the impurity thiosulphate in the product had a great impact on the infrared spectra. The content of thiosulfate becomes lower along with the less absorption peak in the wave range of 1238 ～ 1090 cm-1, as well as the smoother the curve.
Key words：sodium tetrathionate dihydrate; high purity; preparation; characterization
引用本文：刘红梅，谷芳芳，王保金，等. 高纯二水合连四硫酸钠的制备及其表征[J].化学试剂，2023，45（2）：161-165.
