【综述与专论】
基于有机小分子钙离子荧光探针研究进展
张锡钰，林昕烨，林淑芳，谢妍，李达谅*
（福建师范大学 生命科学学院，福建 福州 350117）
摘要：Ca2+是细胞内浓度变化最大的二价阳离子，参与多种生理过程，常作为信号通路中的第二信使。特异性可原位检测Ca2+的方法引发了大量的研究兴趣，取得了不错的进展。其中基于小分子荧光探针的方法具有探针尺寸小、适用原位监测、生物兼容性高等优点备受关注。总结了近年来基于罗丹明、香豆素等小分子为荧光团的Ca2+荧光探针，希望为未来性能更卓越的红外钙离子荧光探针提供强有力的结构活性基础。
中图分类号：O65 文献标识码： A 文章编号：0258-3283（2024）02-0001-09
关键词：钙离子；荧光探针；有机小分子；罗丹明；香豆素；BODIPY
DOI：10.13822/j.cnki.hxsj.2024.0007
Advancements in the Study of Organic Small-Molecule Calcium Ion Fluorescent Probes ZHANG Xi-yu，LIN Xin-ye，LIN Shu-fang，XIE Yan，LI Da-liang* (College of Life Sciences,Fujian Normal University, Fuzhou, 350117 )
Abstract: Ca2+ is a divalent cation with the most significant concentration fluctuations within cells, actively participating in various physiological processes and serving as a second messenger in signal transduction pathways. The development of specific methods for in situ detection of Ca2+ has garnered substantial research interest, leading to considerable progress. Among these approaches, utilizing small-molecule fluorescent probes has attracted attention due to their advantages such as small probe size, suitability for in situ monitoring, and high biocompatibility. This review summarizes recent advancements in Ca2+ fluorescent probes based on small molecules like rhodamine and coumarin. The aim is to provide a robust structural foundation for the future development of high-performance infrared calcium ion fluorescent probes.
Keywords: calcium ions; fluorescent probes; small organic molecules;rhodamine;coumarin; BODIPY
引用本文：引用本文：张锡钰，林昕烨，林淑芳，等.基于有机小分子钙离子荧光探针研究进展[J].化学试剂，2024,46（2）:1-9.
5-取代-4-氨基-3-巯基-1,2,4-三唑衍生物的应用进展
周淑晶，洛雪，柳召宁，蒋雨婷，李进京*
（佳木斯大学 药学院，黑龙江 佳木斯 154007）
摘要：5-取代-4-氨基-3-巯基-1,2,4-三唑是一种重要的五元杂环化合物，由于分子中含有巯基和伯胺基两个活性基团，既可以单个基团参与反应生成N-或S-取代产物，又可以同时发生反应生成稠杂环化合物。由其衍生而来的化合物具有广泛的生物活性，在抗菌、抗肿瘤、抗结核、抗炎镇痛、酶抑制剂、荧光探针等方面都表现出优异的性能。综述了近年来5-取代-4-氨基-3-巯基-1,2,4-三唑衍生物在医学、农业及材料领域中的应用，这为今后此类化合物的进一步研究、开发提供参考。
关键词：5-取代-4-氨基-3-巯基-1,2,4-三唑；衍生物；席夫碱；稠杂环化合物；应用
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283（2024）02-0010-10
DOI：10.13822/j.cnki.hxsj.2023.0658
Application Progress 5-Substituted-4-Amino-3-Mercapto-1,2,4-Triazole Derivatives ZHOU Shu-jing, LUO Xue, LIU Zhao-ning, JIANG Yu-ting, LI Jin-jing*(College of Pharmacy, Jiamusi University, Jiamusi 154007)
Abstract：5-substituted-4-amino-3-mercapto-1,2,4-triazole is an important five-membered heterocyclic compound. Because its molecule contains two active groups, sulfhydryl and primary amine, a single group can participate in the reaction to generate N- or S- substituted products, and it can also react at the same time to generate condensed heterocyclic compounds.The compounds derived from it have a wide range of biological activities, showing excellent properties in antibacterial, antitumor, anti-tuberculosis, anti-inflammatory and analgesic, enzyme inhibitors, fluorescent probes and many other fields. In this paper, the applications of 5-substituted-4-amino-3-mercapto-1,2,4-triazole derivatives medicine, agriculture and materials in recent years are reviewed, which provide reference for the further research and development of such compounds in the future.
Key words：5-substituted-4-amino-3-mercapto-1,2,4-triazole; derivant；schiff base; fused heterocyclic compound; application
引用本文：周淑晶，洛雪，柳召宁，等. 5-取代-4-氨基-3-巯基-1,2,4-三唑衍生物的应用进展[J].化学试剂，2024，46（2）：10-19.
5-羟甲基糠醛选择性加氢制备2,5-二羟甲基呋喃的研究进展
杨拥军*1，黄泽星2，雷婧1，刘贤响2，尹笃林2
（1.郴州高鑫材料有限公司，湖南 郴州 423000；
2.湖南师范大学 化学化工学院 石化新材料与资源精细利用国家地方联合工程实验室，湖南 长沙410081）
摘要：5-羟甲基糠醛（HMF）的催化转化存在产物多样性、反应过程复杂等难点，研究其一步转化为呋喃基C6二元醇对高效利用生物质基化学品发展绿色可降解聚酯新材料具有重要的科学意义。归纳总结了近些年来国内外由HMF制备2,5-二羟甲基呋喃（BHMF）的催化技术研究的新进展，从活性组分、载体及氢供体等方面出发，讨论了不同类型的金属催化剂应用于多相反应催化HMF氢化转化为BHMF时的关键影响因素。对进一步探索如何经济、绿色、高效、可持续地合成BHMF提供理论参考和技术支持。
关键词：生物质；2,5-二羟甲基呋喃；5-羟甲基糠醛；选择加氢；催化
中图分类号：TQ 352.2 文献标识码：A 文章编号：0258-3283（2024）02-0020-08
DOI：10.13822/j.cnki.hxsj.2023.0479
Advances in Catalysts for Selective Hydrogenation of 5-Hydroxymethylfurfural to 2,5- bis(Hydroxymethyl)furan YANG Yong-jun*1,HUANG Ze-xing2,LEI Jing1,LIU Xian-xiang2,YIN Du-lin2 (1. Chenzhou Gao Xin Materials Co., Ltd., Chenzhou 423000, China;2 National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China)
Abstract: Catalytic conversion of 5-hydroxymethylfurfural (HMF) has molecular diversity in products, and its precise conversion to C6 diol has important scientific value and strategic significance for the development of new biodegradable polyester materials. Precent years, it is summarized in this paper that the recent advances in the catalytic technology research on the preparation of 2,5-bis(hydroxymethyl)furan (BHMF) from HMF at home and abroad. The key influencing factors when applied to heterogeneous reaction to catalyze the conversion of HMF into BHMF by the "one-pot method" are analyzed based on the support, active center and hydrogen donor, different types of metal catalysts. There are some theoretical references and technical supports that are purposed for further exploring how to synthesize BHMF economically, green, efficient and sustainable.
Key words: biomass; 2,5-bis(hydroxymethyl)furan; 5-hydroxymethylfurfural; selective hydrogenation; catalysis
引用本文：杨拥军，黄泽星，雷婧，等. 5-羟甲基糠醛选择性加氢制备2,5-二羟甲基呋喃的研究进展[J]. 化学试剂，2024，46(2)：20-27.
【生化与药用试剂】
19F磁共振成像引导的化学动力学/饥饿/化疗协同治疗纳米探针构建及应用
刘晓彤，马景晶，胡高飞*
（北京化工大学 化学学院，北京 100029）
摘要：利用油胺和赖氨酸铜共修饰的聚琥珀酰亚胺两亲高分子（PSILys-Cu-Lys/OAm），实现对全氟冠醚（PFCE，作为氟源）、阿霉素（DOX）的自组装包封，并进一步通过聚赖氨酸（PLL）调节表面静电作用负载葡萄糖氧化酶（GOx），获得DOX/F@PSILys-Cu-Lys/OAm@PLL-GOx（DFPPG）多功能纳米探针，成功将19F磁共振成像（MRI）引导的化学动力学（CDT）/饥饿（ST）/化疗（CT）联合治疗整合于一个纳米平台。体外及活体实验结果表明，探针基于类GOx酶活性有效地催化消耗细胞内葡萄糖转化为H2O2和葡萄糖酸, 不仅可以“饿死”肿瘤, 而且原位自供应H2O2及酸性增强进一步促进了Cu介导的类芬顿反应，增强了CDT。与此同时，探针在肿瘤微酸性环境下响应性释放DOX，解决了化疗药物的生物利用率低问题且降低了探针对正常组织的毒副作用，优异的19FMRI实现了探针（药物）代谢过程的示踪。
关键词：多功能纳米探针；19F磁共振成像； 化学动力学/饥饿/化疗联合治疗；肿瘤
中图分类号：TQ460 文献标识码：A 文章编号：0258-3283（2024）02-0028-11
DOI：10.13822/j.cnki.hxsj.2023.0715
Construction and Application of 19F Magnetic Resonance Imaging-guided Chemodynamic-/Starvation-/Chemotherapy Synergistic Nanoprobes LIU Xiao-tong, MA Jing-jing, HU Gao-fei* (College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China)
Abstract: In this study, the copper lysine and oleylamine-modified polysuccinimide amphiphilic molecule (PSILys-Cu-Lys/OAm) was used to encapsulate and assemble perfluorocarboxane (PFCE, as the fluorine source) and doxorubicin (DOX), further loading glucose oxidase (GOx) via regulation of the surface electrostatic interaction by polylysine (PLL) to obtain DOX/F@PSILys-Cu-Lys/OAm@PLL-GOx multifunctional nanoprobes, thus integrating 19F magnetic resonance imaging (MRI) guided chemodynamic-/ Starvation-/chemo-therapy into a nanoplatform. Both in vitro and in vivo experimental results showed that the probe effectively catalyzed intracellular glucose to generate H2O2 and gluconic acid based on GOx-like activity, which not only "starved" the tumor, but also promoted the Cu-mediated Fenton-like reaction and enhanced CDT by in-situ self-supply of H2O2 and acidic enhancement. At the same time, the as-prepared nanoprobe released DOX in response to the slightly acidic environment of tumor, which solved the problem of low bioavailability of chemotherapy drugs and reduced the toxic side effects of the probe on normal tissues. The excellent 19F MRI realized the tracing of the metabolic process of the probe (drug).
Key words: multi-functional nanoprobes; 19F magnetic resonance imaging; chemodynamic-/ Starvation-/chemotherapy- combined therapy; tumors
引用本文：刘晓彤，马景晶，胡高飞.19F磁共振成像引导的化学动力学/饥饿/化疗协同治疗纳米探针构建及应用[J].化学试剂，2024,46（2）：28-38.
手性螺环氧化吲哚类化合物的设计、合成及抗肿瘤活性研究
张文会,郝知风，李凯，雷胶胶，李亚楠，雷传文*，周英*
（贵州中医药大学 药学院，贵州 贵阳 550025）
摘要：前期利用[2+1]环化反应合成了一系列手性螺环氧化吲哚类化合物，研究采用MTT法，评价此系列化合物对结肠癌细胞CT26和宫颈癌细胞Hela的抗肿瘤活性，探析其构效关系，苗头化合物经结构优化设计合成了目标化合物，并再次评价其抗肿瘤效果。结果表明，27个手性螺环氧化吲哚-环丙烷-茚二酮类化合物对CT26和Hela细胞均具有良好的抗增值作用。其中，16个化合物对CT26细胞的抑制活性优于阳性对照顺铂，14个化合物对Hela细胞的抗增值能力与顺铂相当或更优。进一步，结构优化得到的化合物均能有效抑制CT26和Hela细胞的增值，部分手性螺环氧化吲哚类目标化合物可作为抗肿瘤药物候选先导化合物，具有较好的研发潜力。
关键词：手性螺环氧化吲哚；MTT法；抗肿瘤活性；结构优化；先导化合物
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2024）02-0039-08
DOI：10.13822/j.cnki.hxsj.2023.0569
Design, Synthesis, and Antitumor Activities of Chiral Spirooxindole Compounds ZHANG Wen-hui, HAO Zhi-feng, LI Kai, LEI Jiao-jiao, LI Ya-nan, LEI Chuan-wen*, ZHOU Ying* (Guizhou University of Traditional Chinese Medicine, School of Pharmacy, Guiyang 550025, China)
Abstract: In the early stage, a series of chiral spirooxindole compounds were synthesized by using [2+1] cyclization reaction. In this paper, the MTT method was used to evaluate the antitumor activity of these compounds on colon cancer cell CT26 and cervical cancer cell Hela and their structure-activity relationships were analyzed. The target compounds were synthesized through structural optimization design, and their antitumor effects were evaluated again. The results showed that the 27 chiral spirooxindole cyclopropane indenedione compounds had a good anti proliferative effects on both CT26 and Hela cells. Among them, 16 compounds had a better inhibitory activity on CT26 cells than the positive control cisplatin, and 14 compounds had the same or better anti proliferative ability on Hela cells as cisplatin. Furthermore, the compounds obtained from structural optimization can effectively inhibit the proliferation of CT26 and Hela cells, and some chiral spirooxindole target compounds could be served as candidate lead compounds for antitumor drugs, with good research and development potential.
Keywords: chiral spirooxindole; MTT assays; antitumor activity; structural optimization; lead compound
引用本文：张文会，郝知风，李凯，等.手性螺环氧化吲哚类化合物的设计、合成及抗肿瘤活性研究[J].化学试剂，2024,46（2）：39-46.
【功能材料】
分子印迹材料在手性拆分中的应用研究进展
郑依柳，邵华*，金芬，金茂俊，王静，佘永新*
（中国农业科学院农业质量标准与检测技术研究所，北京 100081）
摘要：拆分手性化合物、提纯有利生物活性的对映异构体在食品、制药、生命科学等领域意义重大。分子印迹聚合物（MIP）是一种人为合成的对目标物质定向亲和的聚合物，基于MIP制造的手性选择剂有更高的亲和力和选择性，并且更容易制备、更稳定，在手性拆分方面应用广泛。综述了MIP材料在手性拆分中用于样品前处理、手性固定相（CSP）、传感器的研究进展，介绍了提高手性选择能力的新策略，包括手性树状大分子、表面印迹载体、金属离子、纳米MIP、手性功能单体、协同辅助材料等，展望了MIP手性拆分未来的发展方向。
关键词：分子印迹聚合物；手性拆分；样品前处理；传感器；手性固定相
中图分类号：O631.3 文献标识码：A 文章编号：0258-3283（2024）02-0047-08
DOI：10.13822/j.cnki.hxsj.2023.0553
Research Progress on Applications of Molecularly Imprinted Materials in Chiral Discrimination ZHENG Yi-Liu, SHAO Hua*, JIN Fen, JIN Mao-Jun, WANG Jing, SHE Yong-Xin* (Institute of Quality Standard and Testing Technology for Agro-products, Chinese Academy of Agricultural Sciences, Beijing 100081, China)
Abstract: Discrimination of chiral substances and purification of enantiomers with favorable biological activity are of great significance in food, pharmaceutical, life science and other fields. Molecularly imprinted polymer (MIP) is an artificially synthesized directional affinity polymer for target substances, which has been widely used in chiral discrimination due to their advantages of higher affinity and selectivity, easier preparation and higher stability. The important applications of MIP in the fields of chiral discrimination for sample pretreatment, chiral stationary phase (CSP) and sensor were emphatically introduced. Then, new strategies to improve chiral selectivity were highlighted, including chiral dendritic macromolecules, surface imprinted carriers, metal ions, nano-MIPs, chiral functional monomers, synergistic auxiliary materials. Finally, the future development direction was prospected.
Key words：molecularly imprinted polymer; chiral discrimination; sample pretreatment; sensor; chiral stationary phase
引用本文：郑依柳，邵华，金芬，等.分子印迹材料在手性拆分中的应用研究进展[J].化学试剂，2024, 46（2）：47-54.
高分散Ag/C3N4的制备及对硝基苯酚催化还原性能的研究
陈兵兵*1,2，解 鹤1，康建1，马 钰1，薛 亮1,2，付 昱*2
（1. 宁夏理工学院 理学与化学工程学院，宁夏 石嘴山753000；2. 东北大学 理学院 化学系，辽宁 沈阳110000）
摘要：金属纳米颗粒的聚集现象严重影响了催化效率，利用简单的方法制备高分散的金属基催化剂还具有一定的挑战性；首先利用柔喷雾技术在液液界面上制备了3种银配位的超分子前驱体膜，即三聚氰胺/三聚氰酸/硝酸银超分子（MC-Ag）、三聚氰胺/巴比妥酸/硝酸银超分子（MB-Ag）和三聚氰胺/三聚氰酸/巴比妥酸/硝酸银超分子（MCB-Ag）；再热缩聚得到高分散的MC-Ag/C3N4、MB-Ag/NC和MCB-Ag/NC这3种银负载材料。在对硝基苯酚的催化还原实验中，MC-Ag/C3N4、MB-Ag/NC和MCB-Ag/NC表观速率常数（Kapp）分别为192.5×10-3 min-1、126.8×10-3 min-1和128.8×10-3 min-1；MC-Ag/C3N4展现出了优良的催化性能，在20 min内催化效率高达99.8%，经过5次循环后催化效果仍保持在97%以上，催化性能主要是MC-Ag/C3N4具有g-C3N4二维结构使银纳米粒子更加分散，更有利于接触更多的活性位点；值得注意的是柔喷雾技术为纳米颗粒的制备和形貌的调控提供了新的思路。
关键词：柔喷雾技术；热缩聚；对硝基苯酚; 催化还原
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2024）02-0055-06
DOI：10.13822/j.cnki.hxsj.2023.0696
Preparation of Highly Dispersed Ag/C3N4 for Catalytic Reduction of P-nitrophenol CHEN Bing-bing*1,2, JIE He1, KANG Jian1, MA Yu1, XUE Liang1，2, FU Yu*2(1. School of Science and Chemical Engineering，Ningxia Institute of Science and Technology, Shizuishan, 753000; 2. Department of Chemistry, College of Science, Northeastern University, Shengyang 110000)
Abstract：The aggregation of metal nanoparticles seriously affects the catalytic efficiency, so it is challenging to prepare highly dispersed metal-based catalysts by simple methods; Firstly, three kinds of silver-coordinated supramolecular precursor films were prepared at the liquid-liquid interface by soft spray technique, namely melamine/cyanuric acid/silver nitrate supramolecular (MC-Ag), melamine/barbituric acid/silver nitrate supramolecular (MB-Ag) and melamine/cyanuric acid/barbituric acid/silver nitrate supramolecular (MCB-Ag). And then obtained highly dispersed MC-Ag/C3N4, MB-Ag/NC and MCB-Ag/NC by thermal polycondensation. In the catalytic reduction of p-nitrophenol, the apparent rate constants (Kapp) of MC-Ag/C3N4, MB-Ag/NC and MCB-Ag/NC were 192.5×10-3 min-1, 126.8×10-3 min-1 and 128.8×10-3 min-1, respectively. MC-Ag/C3N4 has excellent catalytic performance, the catalytic efficiency is as high as 99.8% within 20 min, and the catalytic effect remains above 97% after 5 cycles, mainly due to the g-C3N4 two-dimensional structure of MC-Ag/C3N4, which makes silver nanoparticles more dispersed and more conducive to contact with more active sites. It is worth noting that soft spray technology provides a new idea for the preparation and morphology control of nanoparticles.
Key words：soft spray technology; thermal polycondensation; p-nitrophenol; catalytic reduction
引用本文：陈兵兵，解鹤，康建，等.高分散Ag/C3N4的制备及对硝基苯酚催化还原性能的研究[J].化学试剂，2024，46（2）：55-60.
萘二膦酸锰配位聚合物：合成、晶体结构和磁性质
高文康，徐艳*，李艳，王慧玟，常嘉汶
（宿迁学院 信息工程学院 材料工程系，江苏 宿迁 223800）
摘要：从萘二膦酸配体出发，采用水热法合成了一例萘二膦酸锰配位聚合物：[Mn(1,4-ndpaH2)(4,4-bpy)(H2O)2]·3H2O（1,4-ndpaH4 = 1,4-萘二膦酸，4,4′-bpy = 4,4′-联吡啶），并通过单晶X-射线衍射、元素分析、红外光谱、粉末X-射线衍射及热重分析表征了聚合物的结构和热稳定性。单晶结构分析表明，目标聚合物中金属MnII离子呈六配位畸变的八面体几何构型，相邻的金属MnII离子由辅助配体4,4′-bpy连接成一维链，这些一维链再进一步通过萘膦酸配体连接成二维层状结构，结晶水分子填充在层间空隙内，通过氢键和范德华作用力固定于骨架结构中。目标聚合物的磁学性质研究表明，MnII离子之间存在反铁磁相互作用。
关键词：萘二膦酸；锰配合物；晶体结构；磁性质
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2024）02-0061-06
DOI：10.13822/j.cnki.hxsj.2023.0636
Naphthalene Bisphosphonate Manganese Coordination Polymer: Synthesis, Crystal Structure, and Magnetic Properties GAO Wen-kang, XU Yan*, LI Yan, WANG Hui-wen, CHANG Jia-wen (Department of Materials Engineering, Institute of Information Engineering, Suqian University, Suqian 223800, China)
Abstract：Starting from naphthalene bisphosphonic acid ligand, a novel manganese phosphonate coordination polymer, [Mn(1,4-ndpaH2)(4,4-bpy)(H2O)2]·3H2O (1), was synthesized using hydrothermal method (1,4-ndpaH4 = 1,4-naphthalene bisphosphonic acid, 4,4′-bpy = 4,4′-bipyridine). The structure and thermal stability of the polymer were characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. Single crystal structure analysis shows that the metal MnII ions in target polymer displays a distorted octahedral environment, and adjacent MnII ions are connected into one-dimensional chains by the auxiliary ligand 4,4′-bpy, and further connected into two-dimensional layered structures through naphthalene phosphonic acid ligands. Water molecules are filled in the interlayer spaces and fixed in the framework structure through hydrogen bonds and van der Waals forces. The magnetic properties study of target polymer shows that there is antiferromagnetic interaction between MnII ions.
Key words：naphthalene bisphosphonate; manganese coordination polymer; crystal structure; magnetic property
引用本文：高文康，徐艳，李艳，等.萘二膦酸锰配位聚合物：合成、晶体结构和磁性质[J].化学试剂，2024,46（2）：61-66.
【分离提取技术】
大别山艾叶多糖提取工艺优化及其吸湿保湿、抗氧化性能研究
陈卫1a,2，谷彩花1b，叶兆伟1a,2，熊林斌2，李涛2，郜雅婧1a，陈琼*1a,2
（1. 信阳农林学院 a. 制药工程学院；b. 农学院，河南 信阳 464000；
2.河南省大别山艾草综合开发利用工程技术研究中心，河南 信阳 464000）
摘要：为挖掘大别山艾草的应用价值，开发出更多艾草相关产品，促进大别山革命老区经济社会发展。采用正交试验优化超声波-酶法提取大别山艾叶多糖工艺，并对艾叶多糖的吸湿保湿和抗氧化性能进行测定。试验结果表明，大别山艾叶多糖的最佳提取工艺为料液比1∶35 （g/mL）、纤维素酶添加量1%、超声时间25 min，在该条件下，艾叶多糖提取率为1.72%。在相对湿度为43%的环境下，大别山艾叶多糖的吸湿率为35.7%；在相对湿度为81%的环境下，吸湿率为40.3%；在干燥环境下，保湿率为66.9%。大别山艾叶多糖对DPPH自由基和羟基自由基都有清除作用，在浓度为1.2 mg/mL对DPPH自由基的清除率为28.5%，对羟基自由基的清除率为30.4%。大别山艾叶多糖具有良好的吸湿和保湿性能，并且具有一定的抗氧化活性，可以开发其作为一种天然的食品添加剂。
关键词：艾叶多糖；纤维素酶；吸湿；保湿；抗氧化
中图分类号：TQ28 文献标识码：A 文章编号：0258-3283（2024）02-0067-07
DOI：10.13822/j.cnki.hxsj.2023.0655
Study on Extraction Optimization of Artemisia argyi Polysaccharides in Dabie Mountain and Its Moisture-absorption-retention and Antioxidant Properties CHEN Wei1a,2, GU Cai-hua1b, YE Zhao-wei1a,2, XIONG Lin-bin2, LI Tao2, GAO Ya-jing1a, CHEN Qiong*1a,2 (1.a. School of Pharmaceutical Engineering, b. Xinyang Agriculture and Forestry University, College of Agronomy, Xinyang 464000, China; 2. Dabie Mountain Mugwort Comprehensive Development and Utilization Engineering Technology Research Center of Henan Province, Xinyang 464000, China)
Abstract: In order to tap the application value of Artemisia argyi in Dabie Mountain, more wormwood related products have been developed to promote the economic and social development of the old revolutionary area of Dabie Mountain. The process of extracting Dabie mugwort leaf polysaccharides by ultrasonic-enzymatic method was optimized by orthogonal test, and the hygroscopic, moisturizing and antioxidant properties of mugwort leaf polysaccharides were measured. The experimental results showed that the optimal extraction process of Dabie Mountain wormwood leaf polysaccharide was 1∶35 g/mL, cellulase addition 1%, and ultrasonic time of 25 min, under which the yield of mugwort leaf polysaccharide was 1.72%. In the environment of relative humidity of 43%, the moisture absorption rate of Dabie Mountain mugwort leaf polysaccharide was 35.7%, in the environment of 81% relative humidity, the moisture absorption rate was 40.3%, and in the dry environment, the moisture absorption rate was 66.9%. Dabie Shan mugwort leaf polysaccharide has a scavenging effect on DPPH radicals and hydroxyl radicals, and the scavenging rate of DPPH radicals at a concentration of 1.2 mg/mL is 28.5%, and the scavenging rate of p-hydroxy radicals is 30.4%. Dabie Mountain mugwort leaf polysaccharide has good hygroscopic and moisturizing properties, and has certain antioxidant activity, which can be developed as a natural food additive.
Key words: Artemisia argyi polysaccharides; cellulase; moisture absorption; moisture retention; antioxidant
引用本文：陈卫，谷彩花，叶兆伟，等.大别山艾叶多糖提取工艺优化及其吸湿保湿、抗氧化性能研究[J].化学试剂，2024,46（2）：67-73.
【电化学和新能源】
可控设计的Co-N/C电催化剂及其氧还原反应活性
胡鹏*1，张琪婧2，路肖栋1，左自豪1
(1. 黄淮学院 化学与制药工程学院，河南 驻马店 463000；2. 沈阳化工大学 理学院，辽宁 沈阳 110142)
摘要：能源问题是事关国家发展和安全的重大问题，氧还原反应作为燃料电池阴极半反应近年来成为能源和电催化领域的研究热点之一。利用2, 9-二甲基-1, 10-邻菲啰啉与钴离子配位形成配合物，配合物与炭黑混合均匀，经中温热解和浓硝酸氧化后得到钴、氮表面修饰的碳负载纳米催化剂Co-N/C。实验首先利用旋转圆盘电极和旋转环盘电极(RRDE)考察了催化剂在不同pH值下的电催化氧还原性能。电化学测试结果显示，催化剂在碱性条件下具有与商业Pt/C相近的4电子氧还原催化性能。随后，实验借助SEM、TEM、XPS、XRD和FT-IR等设备对催化剂进行表征，以揭示Co-N/C催化剂四电子氧还原催化活性增强的起源。本工作运用功能化修饰策略调控碳材料表面的催化活性位点和碳的电子结构，克服了本征碳材料催化活性不高的缺点，为设计新型非贵金属氧还原反应催化剂提供了一种新的思路。
关键词：Co-N/C；热解；表面调控；电催化剂；氧还原反应；
中图分类号：TQ138.1 文献标识码：A 文章编号： 0258-3283（2024）02-0074-06
DOI：10.13822/j.cnki.hxsj.2023.0605
Controllable Design of Co-N/C Electrocatalyst and Its Oxygen Reduction Activity HU Peng*1, ZHANG Qi-jing2, LU Xiao-dong1, ZUO Zi-hao1 (1. College of Chemistry and Pharmaceutical Engineering, Huanghuai University, Zhumadian 463000, China; 2. College of Science, Shenyang University of Chemical Technology, Shenyang 110142, China)
Abstract：Energy issue is a major concern related to national development and security. In recent years, oxygen reduction reaction, as a cathode half reaction of fuel cell, has become one of the research hotspots in the field of energy and electrocatalysis. In this study, 2, 9-dimethyl-1, 10-phenanthroline were used to coordinate with cobalt ions to form a complex. The complex was uniformly mixed with carbon black. After medium temperature pyrolysis and concentrated nitric acid oxidation, cobalt and nitrogen surface-modified carbon supported nanocatalyst Co-N/C was obtained. Firstly, the electrocatalytic oxygen reduction performance of the catalyst at different pH values was investigated by rotating disk electrode and rotating ring disk electrode. Electrochemical test results show that the catalyst has a four-electron oxygen reduction catalytic performance, which is similar to that of commercial Pt/C under alkaline conditions. Subsequently, the Co-N/C catalyst was characterized by SEM, TEM, XPS, XRD and FT-IR to reveal the origin of the enhanced four-electron oxygen reduction catalytic activity. In this work, functional modification strategies were used to regulate the catalytic active sites and the electronic structure of surface carbon atoms, which overcame the shortcomings of low catalytic activity of intrinsic carbon materials, and provided a new insight for the design of novel non-noble metal oxygen reduction catalysts.
Key words：Co-N/C; pyrolysis; surface regulation; electrocatalyst; oxygen reduction reaction
引用本文：胡鹏，张琪婧，路肖栋，等.可控设计的Co-N/C电催化剂及其氧还原反应活性[J].化学试剂，2024,46（2）：74-79.
【化学品与环境】
金属基吸附剂除氟技术及吸附机理研究进展
崔小梅，肖方景，赵远昭，魏延丽，谢民生，布多*，张强英*
（西藏大学 生态环境学院，西藏 拉萨 850000）
摘要：氟化物是水污染评价的重要指标之一，高浓度氟化物对饮用水安全构成了威胁，因此开发高效、低成本、高选择性的除氟技术是当前研究的重点。在沉淀、膜分离、离子交换、电絮凝和吸附等除氟技术中，吸附除氟是目前最有前景的技术之一。众多吸附材料中，金属基吸附剂因独特的结构和形貌、优异的吸附性能，被广泛应用于水体除氟研究。综述了铝、铁、稀土基等典型金属吸附剂的开发和改性，阐述了金属基吸附剂制备工艺的强化方法，对比分析了各类金属基吸附剂性能的影响因素，总结了金属基吸附剂的吸附机理和再生技术，提出了金属基吸附剂在除氟领域存在困难和未来发展趋势，为后续金属基吸附剂的开发改性、工艺强化提供理论参考。
关键词: 氟；金属基吸附剂；开发和改性；工艺强化；吸附机理
中图分类号: X522 文献标识码: A 文章编号: 0258-3283（2024）02-0080-08
DOI：10.13822/j.cnki.hxsj.2023.0673
Research Progress on Fluorine Removal Technology and Adsorption Mechanism of Metal-based Adsorbents CUI Xiao-mei，XIAO Fang-jing，ZHAO Yuan-zhao，WEI Yan-li，XIE Min-sheng， BU Duo*，ZHANG Qiang-ying* (School of Ecology and Environment, Tibet University, Lhasa, 850000, China)
Abstract：Fluoride plays a crucial role in assessing water pollution, especially concerning drinking water safety at elevated concentrations. Consequently the current research emphasizes the development of fluoride removal technologies that are efficient, cost-effective, and highly selective. Among various methodologies for fluoride removal, including precipitation, membrane separation, ion exchange, and electroflocculation, adsorption stands out as a particularly promising techniques. Metal-based adsorbents, such as aluminium, iron, and rare earth-based materials, have gained widespread attention due to their unique structural and morphological characteristics, along with superior adsorption performance in water fluoride elimination. This paper provides a comprehensive review of the evolution and enhancement of emblematic metal-based adsorbents. It details the methods employed to enhance the fabrication process of these adsorbents, compares and analyzes variables impacting the efficiency of diverse metal-based adsorbents, and encapsulates the adsorption mechanisms and regeneration technology associated with them. Furthermore, the article highlights the challenges and prospective developmental trends of metal-based adsorbents in the field of fluoride removal. This serves as a valuable reference for subsequent research on the refinement and development of metal-based adsorbents and process intensification.
Key words：fluorine; metal-based adsorbents; development and modification; process enhancement; adsorption mechanism
引用本文：崔小梅，肖方景，赵远昭，等.金属基吸附剂除氟技术及吸附机理研究进展[J].化学试剂，2024,46（2）：80-87.
一种适用于检测水相中肼的荧光探针研究
王磊*1，李雪1，吴佳佳1，刘佳蕊1，陈奕辛1，甘静1，张文静2
（1. 许昌学院 数理学院，河南 许昌 461000；
2. 郑州大学 化学学院（绿色催化中心），河南 郑州 450001）
摘要：肼是一种重要的化工原料，具有非常广泛的用途。肼的毒性对环境和生物体具有重要影响，然而能够检测水相中肼的荧光探针非常有限。设计合成了一种新的反应型荧光探针，使用核磁共振和高分辨质谱对中间产物和探针分子进行了结构表征。研究发现探针能够特异性的检测水相中的肼，具有较高的灵敏度和强抗干扰能力。通过荧光光谱和理论计算相结合，探究了探针的检测机理和发光性质。研究发现探针分子与肼接触，发生肼解反应，荧光团恢复激发态分子内质子转移（ESIPT）发光，从而实现对肼的特异性检测。
关键词：荧光探针；肼；水相；ESIPT；理论计算
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2024）02-0088-07
DOI：10.13822/j.cnki.hxsj.2023.0657
Research of a Fluorescent Probe Detecting for Hydrazine in Water Phase WANG Lei*1, LI Xue1, WU Jia-jia1, LIU Jia-rui1, CHEN Yi-xin1, GAN Jing1, ZHANG Wen-jing2(1. School of Science, Xuchang University, Xuchang 461000, China; 2. Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China)
Abstract: Hydrazine is an important chemical raw material and has a wide range of applications. The toxicity of hydrazine has important effects on the environment and organisms. However, fluorescent probes capable of detecting hydrazine in the water phase are very limited. A new reactive fluorescence probe was designed and synthesized. The intermediate and probe were characterized by NMR and high-resolution mass spectrometry. It was found that the probe can specifically detect hydrazine in water phase, with high sensitivity and strong anti-interference ability. The detection mechanism and luminescence properties of the probe were investigated by combining fluorescence spectra and theoretical calculation. It was found that the probe molecules mixed with hydrazine, the hydrazolysis reaction occurred, and the fluorophore recovers luminescence of ESIPT process, to achieve the specific detection of hydrazine.
Key words: fluorescent probe; hydrazine; water phase; ESIPT; theoretical calculation
引用本文：王磊，李雪，吴佳佳，等. 一种适用于检测水相中肼的荧光探针研究[J]. 化学试剂，2024，46（2）：88-94.
【分析与测试】
基于UPLC-Q-Orbitrap MS技术的沙棘黄酮类成分分析
杨祖凡1,2，王倩1,2，赵晴1,2，李燕红1,2，贾强强*1,2
（1. 青海大学 医学院 药学系，青海 西宁 810001
2. 青海大学三江源生态与高原农牧业国家重点实验室，青海 西宁 810016）
摘要：利用UPLC-Q-Orbitrap MS技术对沙棘（Hippophae rhamnoides L.）果实中黄酮类物质进行系统剖析，并对不同产地沙棘果实中黄酮类化合物进行比较分析，为中药沙棘的化学物质基础和资源利用研究奠定基础。根据保留时间比对，精确分子量匹配和MS/MS碎片信息分析，共鉴定出58个化合物，包括34个黄酮醇、4个黄酮、14个花色素、1个二氢黄烷酮、2个二氢黄烷醇、2个黄烷醇和1个二氢查尔酮，其中14个花色素类化合物为首次在沙棘果实中鉴定。最终筛选得到38种差异积累的黄酮类化合物，其中大部分在青海和西藏产地的沙棘果中呈显著积累。研究丰富了沙棘果中黄酮类化合物化学物质基础研究，揭示了不同产地沙棘果中黄酮类化合物的组成及差异。
关键词：黄酮；沙棘；定性分析；UPLC-Q-Orbitrap MS；化学计量学
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）02-0095-12
DOI：10.13822/j.cnki.hxsj.2023.0726
Identification and Characterization of Flavonoid Compounds from Hippophae rhamnoides L. by UPLC-Q-Orbitrap MS YANG Zu-fan 1, 2, WANG Qian 1, 2, ZHAO Qing 1, 2, LI Yan-hong 1, 2, JIA Qiang-qiang* 1, 2 (1. Department of Pharmacy, Medical College ,Qinghai University, Xining, 810001, China; 2. State Key Laboratory of Plateau Ecology and Agriculture, Qinghai University, Xining, 810016, China)
Abstract: The flavonoids in the fruits of Hippophae rhamnoides L. were systematically analyzed by UPLC-Q-Orbitrap MS technique, and the flavonoids in the fruits of Hippophae rhamnoides L. from different producing areas were compared and analyzed, which laid a foundation for the research on the chemical substance basis and resource utilization of traditional Chinese medicine Hippophae rhamnoides L. Based on retention time comparing, precise molecular weight matching and MS/MS fragment information analysis, a total of 58 compounds were identified, including 34 flavonols, 4 flavones, 14 anthocyanins, 1 dihydroflavanone, 2 dihydroflavanols, 2 flavanols and 1 dihydrochalcones. Among them, 14 anthocyanins were identified for the first time in Hippophae rhamnoides L. fruits. A total of 38 differentially accumulated flavonoids were finally screened, most of which were significantly accumulated in Hippophae rhamnoides L. fruits from Qinghai and Tibet. This study enriched the basic research of flavonoids in Hippophae rhamnoides L. fruit, and revealed the composition and differences of flavonoids in Hippophae rhamnoides L. fruit from different regions.
Key words: flavonoid compounds; Hippophae rhamnoides L.; qualitative analysis; UPLC-Q-Orbitrap MS; chemometrics
引用本文：杨祖凡，王倩，赵晴，等. 基于UPLC-Q-Orbitrap MS技术分析沙棘果实中黄酮类成分[J]. 化学试剂，2024，46（2）：95-106.
【标准物质与标准品】
痕量甲基肼标准气体的研制及其不确定度评定
慕晓刚1，朱天一2，许峰2，王煊军*1
（1.火箭军工程大学 智剑实验室，陕西 西安 710025；2.中国兵器工业集团第五三研究所，山东 济南 250031）
摘要：基于渗透法原理建立了痕量甲基肼标准气体发生方法及不确定度评定模型，采用预先测定过的高纯度甲基肼为原料，并通过自动称量定值的方式，制备出符合拟研制标准气体渗透率要求的渗透管，采用载有渗透管的多功能气体校准装置实现了标准气体的产生。采用GUM法对渗透管渗透率的不确定度进行了评定，采用MCM法对甲基肼标准气体量值的不确定度进行了评定，其相对扩展不确定度小于5%，该标准物质对甲基肼气体检测仪的校准与性能评价具有实用价值。
关键词：标准气体；甲基肼；渗透法；不确定度评定；蒙特卡洛法
中图分类号：TQ421 文献标识码：A 文章编号：0258-3283（2024）02-0107-07
DOI：10.13822/j.cnki.hxsj.2023.0641
Preparation of Trace MMH Gas Reference Material and Evaluation for Uncertainty MU Xiao-gang1, ZHU Tian-yi2, XU Feng2, WANG Xuan-jun*1 (1.Zhijian Laboratory, Rocket Force University of Engineering, Xi’an 710025, China;2.CNGC Institue 53, Ji’nan 250031, China)
Abstract:The generation method and uncertainty evaluation model of trace methylhydrazine standard gas were established based on the principle of permeation method. The pre-measured high-purity methylhydrazine was used as raw material, and the permeation tube that met the permeability requirements of the standard gas to be developed was prepared by means of automatic weighing and fixed value. The multifunctional gas calibration device equipped with permeation tube was used to realize the generation of standard gas. The GUM method was used to evaluate the uncertainty of the permeability of the permeation tube, and the MCM method was used to evaluate the uncertainty of the methylhydrazine standard gas value. The relative expanded uncertainty is less than 5%. This standard material has practical value for the calibration and performance evaluation of the methylhydrazine gas detector.
Key words:gas reference material; monomethylhydrazine; permeation method; uncertainty; monte carlo method
引用本文：慕晓刚，朱天一，许峰，等.痕量甲基肼标准气体的研制及其不确定度评定[J].化学试剂，2024,46（2）：107-113.
【合成与工艺技术】
含乙基咔唑基团钌化合物的合成及其抗菌活性研究
宋允，黄紫莹，余光英，林文静，姜桂娟，王金涛*，廖向文*
(江西科技师范大学 药学院，江西 南昌 330013)
摘要：以乙基咔唑取代的邻菲啰啉衍生物为主配体(ECYMP)合成了4个新型抗菌钌化合物，通过最低抑菌浓度、最低杀菌浓度、溶血实验、生物膜清除试验、DNA泄露试验、大蜡螟幼虫以及小鼠感染模型对化合物的抗菌活性、安全性、耐药性和抗菌机制进行了评价。结果表明：4个钌配合物均具有显著的抗菌活性，化合物Ru-2能通过破坏细菌细胞膜的完整性杀死细菌。此外，Ru-2不仅能有效抑制细菌毒素的分泌，而且具有较高的安全性。在动物感染模型中，Ru-2亦呈现出显著的抗感染活性。结论：具有乙基咔唑功能化配体的钌化合物具有显著的体内外抗菌活性。
关键词：金黄色葡萄球菌；钌配合物；乙基咔唑；抗菌；
中图分类号：R916 文献标识码：A 文章编号： 0258-3283（2024）02-0114-07
DOI：10.13822/j.cnki.hxsj.2023.0572
Synthesis and Antibacterial Activity of Ruthenium Compounds Containing Ethylcarbazole Groups SONG Yun, HUANG Zi-ying,YU Guang-ying,LIN Wen-jing,JIANG Gui-juan, WANG Jin-tao*, LIAO Xiang-wen* (School of pharmacy, jiangxi science and technology normal university, nanchang 330013, China)
Abstract：Four novel antibacterial ruthenium compounds bearing ethyl carbazole were synthesized. Their antibacterial activity, safety, resistance frequencies and mode of action were evaluated by minimum inhibitory concentration, minimum bactericidal concentration, hemolytic toxin test, biofilm eradication, DNA leakage assay, G. melonella larvae and mouse infection model. The results indicated that four complexes all exhibited significant antibacterial activity, and Ru-2 could kill bacteria by destroying the bacterial cell membrane. In addition, Ru-2 not only effectively inhibits the secretion of bacterial toxins, but also exhibited low toxicity. More importantly, Ru-2 also exhibited robust anti-infective potency in animal infection model. In summary, our study suggested that ruthenium compounds bearing with ethyl carbazole functionalized ligand have remarkable antibacterial potency in vitro and in vivo.
Key words：Staphylococcus aureus; ruthenium compounds; ethylcarbazole; antibacterial
引用本文：宋允，黄紫莹，余光英,等.含乙基咔唑基团钌化合物的合成及其抗菌活性研究[J].化学试剂，2024,46（2）：114-120.
新型苦参碱C-14腙类衍生物的合成及抗肿瘤活性研究
伍亚晴a，李金坪a，王立升*b
（广西大学a.化学化工学院,b.医学院，广西 南宁 530004）
摘要：以苦参碱为先导化合物，设计并合成了16个苦参碱腙类衍生物，均通过1HNMR、13CNMR和HR-MS进行了结构表征。通过MTT比色法进行体外抗增殖活性实验，测试了所有目标化合物对人宫颈癌细胞HeLa、人结肠癌细胞HCT116和非小细胞肺癌细胞A549这3种细胞的活性，部分目标化合物对上述细胞表现出良好的抗增殖活性，并优于苦参碱，其中活性最好的化合物为14-（（（4-叔丁基苄基）-1H-吲哚-3-亚甲基）肼亚甲基）苦参碱，其对3种细胞IC50值分别为（11.65±0.28）、（9.14±0.81）和（14.48±0.63）mmol/L，对HCT116细胞的抗增殖活性最强，细胞周期实验结果表明，目标化合物对HCT116细胞周期阻滞在G0/G1期。分子对接结果表明，该化合物与蛋白6QJX存在氢键和p-p堆积作用等相互作用力。
关键词：苦参碱；腙类；衍生物；合成；抗肿瘤
中图分类号：O626.4 文献标识码：A 文章编号：0258-3283（2024）02-0121-09
DOI：10.13822/j.cnki.hxsj.2023.0689
Synthesis and Antitumor Activity of Novel Matrine C-14 Hydrazone Derivatives Wu Ya-qinga, Li Jin-pinga, Wang Li-sheng *b (a. School of Chemistry and Chemical Engineering, b. School of Medicine, Guangxi University, Nanning 53004, China)
Abstract: Sixteen matrine hydrazone derivatives were designed and synthesized using matrine as the lead compound. Their structures were characterized by 1HNMR, 13CNMR and HR-MS. The anti-proliferative activities of all target compounds on three cell lines, human cervical cancer cell HeLa, human colon cancer cell HCT116 and non-small cell lung cancer cell A549, were tested by MTT colorimetric assay in vitro. Some of the target compounds showed good anti-proliferation activity against the above cells, and were superior to matrine. The compound with the best activity was 4i.14- (((4-tert-butylbenzyl) -1h-indole-3-methylene) hydrazine methylene) matrine. The IC50 values for the three kinds of cells were（11.65±0.28）mmol/L, （9.14±0.81）mmol/L and （14.48±0.63）mmol/L, respectively, and it had the strongest anti-proliferation activity against HCT116 cells. The results of cell cycle experiment showed that compound 4i blocked HCT116 cell cycle in G0/G1 phase. The molecular docking results indicated the presence of interaction forces such as hydrogen bonding and p-p stacking interaction between compound 4i and protein 6QJX.
Key words: matrine; hydrazone; derivative; synthesis; antitumor
引用本文：伍亚晴，李金坪，王立升.新型苦参碱C-14腙类衍生物的合成及抗肿瘤活性研究[J].化学试剂，2024,46（2）：121-129.
