【综述与专论】
核酸适配体传感器在血小板衍生生长因子检测中应用进展
杨柳，王乐乐，陶晴，孟娇然，丁敏，李兰英*，刘刚
(上海市计量测试技术研究院 国家市场监管重点实验室（生物分析计量溯源），上海 201203)
摘要：血小板衍生生长因子（Platelet Derived Growth Factor，PDGF）是一种低分子量碱性蛋白质，其中PDGF-BB亚型是诊断和识别癌症的重要的生物标志物蛋白，与多种疾病的诊断相关，包含肝纤维化、动脉粥样硬化、老年性黄斑变性和糖尿病性眼病等。同时，PDGF-BB是一种具有多种生物学功能的细胞因子，被公认为伤口愈合和组织修复的药物。传统的PDGF-BB检测方法包括酶联免疫吸附法等在内的方法耗时长、成本高、仪器复杂等不足限制了其实际应用。近年来，核酸适配体传感器以其高特异性、高灵敏度、低成本、响应速度快等优点在PDGF-BB检测方面引起科学家们越来越多的关注。本文综述了近年来检测PDGF-BB的核酸适配体传感器研究进展，以期为今后基于核酸适配体的PDGF-BB生物传感检测方法的设计提供参考。
关键词：PDGF-BB；核酸适配体传感器；电化学法；荧光法；比色法
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2023.0020
Application Progress of Aptamer-based Sensors in Detection of PDGF-BB YANG Liu, WANG Le-le, TAO Qing, MENG Jiao-ran , DING Min, LI Lan-ying*, LIU Gang (Key Laboratory of Bioanalysis and Metrology for State Market Regulation, Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China)
Abstract：Platelet derived growth factor (PDGF) is a basic protein with low molecular mass and its subtype BB (PDGF-BB) commonly serves as an important protein biomarker for diagnosis and recognition of cancer, which has been implicated in various diseases, including liver fibrosis, atherosclerosis, age-related macular degeneration and diabetic eye disease. Furthermore, PDGF is a significant cytokine with multiple biological functions, which has been accepted as a chief medicine in wound healing and tissue repair. Traditional detection methods of PDGF-BB including enzyme-linked immunosorbent assay are time-consuming, costly, and complicated, thereby limiting their usefulness and making them impractical to implement at the point of care. In recent years, aptamer-based sensors have attracted more and more attention from scientist in the detection of PDGF-BB due to their high specificity,high sensitivity, low cost and fast response. The review summarized recent advances in the development of various aptamer-based sensors for PDGF-BB detection with the aim to provide a general guide for the design of aptamer-based sensitive biosensing assays for PDGF-BB in the future.
Key words：PDGF-BB; aptamer-based sensor; electrochemical method; fluorescence method; colorimetric method
引用本文：杨柳，王乐乐，陶晴，等. 核酸适配体传感器在血小板衍生生长因子检测中应用进展[J]. 化学试剂, 2023, 45(5): 1-10。
基于BODIPY的荧光探针检测活性氧的研究进展
赖申枝1，谢俊英*1，李春艳2，刘燕1，肖洁1
（1. 湖南化工职业技术学院 制药与生物工程学院，湖南 株洲 412000；2. 湘潭大学 化学学院，湖南 湘潭 411105）
摘要：活性氧（ROS）是一种重要的含氧化学活性物质，与各种生理过程密切相关。但过量的ROS可能会导致诸多疾病，如心血管疾病、神经退行性疾病甚至癌症等，因此有效的识别和检测ROS具有重要意义。氟硼二吡咯亚甲基（BODIPY）由于其独特的光物理性质、优异的光化学稳定性以及可行的衍生化，近年来被广泛应用于检测ROS。针对不同的活性氧进行分类，主要综述了近5年来国内外基于BODIPY荧光探针用于检测ROS的研究现状，并展望了BODIPY荧光探针检测ROS的发展方向，旨在为今后研究ROS在生理和病理过程中的作用提供一定的理论参考。
关键词：活性氧；BODIPY；荧光探针；检测；研究进展
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0034
Recent Developments of BODIPY-based Fluorescent Probes for the Detection of Reactive Oxygen LAI Shen-zhi1, XIE Jun-ying*1, LI Chun-yan2, LIU Yan1, XIAO Jie1 (1. Department of Pharmaceutical and Biological Engineering, Hunan Chemical Vocational Technology College, Zhuzhou 412000, China; 2. College of Chemistry, Xiangtan University, Xiangtan 411105, China)
Abstract: Reactive oxygen species (ROS) are important oxygen-containing chemical active substance, which are closely related to various physiological processes. But excessive ROS may cause many diseases, such as cardiovascular disease, neurodegenerative disease, and even cancer. Thus the effective identification and detection of ROS is of great importance. Due to the unique photophysical properties, excellent photochemical stability and feasible derivatization, boron-fluoropyrrolidine methylene (BODIPY) has been widely used for ROS detection in recent years. This article classifies different ROS, mainly reviews the research status of BODIPY-based fluorescence probes for ROS detection at home and abroad in the past five years, prospects the development direction of BODIPY-based fluorescence probe for detection of ROS, and provides some reference value for future research on the role of ROS in the physiopathological process.
Key words: ROS; BODIPY; fluorescent probes; detection; research progress
引用本文：赖申枝, 谢俊英, 李春艳, 等. 基于BODIPY的荧光探针检测活性氧的研究进展[J]. 化学试剂, 2023, 45（5）：11-20.
酸致变色染料的应用研究进展
孟德泉，单斌*，谭伟强，马继平
（青岛理工大学 环境与市政工程学院，山东 青岛 266520）
摘要：酸致变色染料是指在一定范围内其颜色可随pH值的改变发生可逆变化的一类功能染料。基于酸致变色染料开发的pH传感器，可广泛应用于生物工程、健康监测、食品安全、环境监测等研究领域。按照染料的结构类型，简要介绍了酸致变色染料的变色机理，详细总结了近几年在相关领域的应用研究进展。最后对该类染料的发展方向进行了展望，旨在为酸致变色染料的设计开发和应用研究提供新的视角。
关键词：酸致变色染料；pH指示剂；变色机理；pH传感器
中图分类号：TQ617 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0043
Research Progress in the Application of Halochromic Dyes MENG De-quan, SHAN Bin*, TAN Wei-qiang, MA Ji-ping（School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520, China）
Abstract: Halochromic dyes are a kind of functional dye, the color of which can change reversibly with the change of pH value in a certain range. A series of pH sensors explored from halochromic dyes can be widely used in biological engineering, health monitoring, food safety, environmental monitoring, and other research fields. According to the classification of dyes, the mechanisms of halochromic dyes are briefly introduced and the application research progress in related fields in recent years is summarized in detail. Finally, the development direction is prospected, with the aim to provide a new perspective for the design and application of halochromic dyes.
Key words: halochromic dyes; pH indicators; discoloration mechanism; pH sensors
引用本文：孟德泉，单斌，谭伟强，等. 酸致变色染料的应用研究进展[J]. 化学试剂, 2023, 45(5): 21-32。
烯烃配位聚合的链转移反应以及应用
刘照贺
(中石化（北京）化工研究院有限公司，北京，100013)
摘要：链转移反应在烯烃配位聚合过程中占据重要位置，不仅可以控制聚合物的分子量，甚至还可以利用链转移反应调控聚合物的拓扑结构，本综述从均相催化剂催化烯烃配位聚合过程中的链转移反应为切入点，讨论了常见的链转移反应、向催化体系加入合适的链转移剂合成功能化基团封端的聚烯烃、配位聚合中聚合物链向溶剂甲苯转移的新颖链转移反应，以及通过链转移反应控制聚合物拓扑结构的机理，最后以氢气（H2）为链转移剂，分别讨论了对非均相催化剂催化乙烯和丙烯聚合活性的影响机制。
关键词：链转移反应；均相催化剂；非均相催化剂；分子量；拓扑结构
中图分类号：O632.12 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0007
Chain Transfer Reactions and Applications in Olefin Coordination Polymerization LIU Zhao-he (SINOPEC (Beijing) Research Institute of Chemical Industry Co., Ltd., Beijing 100013, China)， Huaxue Shiji, 2023
Abstract: Chain transfer reaction plays an important role in coordination polymerization, which do not only control the average molecular weight of the polymer, the topology of the polymer can also be regulated. This review starts from the chain transfer reactions in coordination polymerization by using homogeneous catalyst, discuss respectively the usual mode of the chain transfer reactions, the synthesis of chain-end functionalized polyolefin by adding the proper chain transfer agent to the catalytic system, chain transferring to solvent toluene in coordination polymerization as a novel mode, the mechanism of chain transfer reactions affecting polymer topology. In the end, the influence mechanism of H2 as chain transfer agent in the polymerization activity of ethylene and propylene by using heterogeneous catalyst is discussed in detail.
Key words: chain transfer reactions; homogeneous catalyst; heterogeneous catalyst; average molecular weight; topology
引用本文：刘照贺. 烯烃配位聚合的链转移反应以及应用[J]. 化学试剂, 2023,45（5）：33-40.
【生化与药用试剂】
三萜类化合物结构修饰及活性研究进展
何诗能a，张清a，谭珍媛b，谢云峰a，邱莉a，谢集照*a
(广西医科大学 a.药学院；b.高等职业技术学院，广西 南宁 530021)
摘要：三萜类化合物在天然产物中广泛存在，含量丰富，是许多药用植物的主要活性成分之一。早在上世纪30年代就有关于三萜的研究，该类物质以其显著的活性与广泛的药理作用受到研究者的青睐。近年来关于三萜及其衍生物的合成是受人关注的研究热点。三萜的结构修饰多以四环三萜及五环三萜为起始物，针对四环三萜的修饰位点主要在A环C-2、C-3位及D环上的侧链，多引入羟基、酯基或含氮基团等。针对五环三萜的修饰主要在A环C-2、C-3位及C-28位，主要有酯化、酰胺化及引入含氮结构等修饰，还有部分非常见的修饰位点同样对活性有重要影响。综述了三萜及其衍生物的结构修饰与活性变化研究进展，为三萜的合成修饰与进一步开发利用提供参考。
关键词：四环三萜；五环三萜；结构修饰；活性；衍生物
中图分类号：R96 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0811
Research Progress on Structural Modification and Biological Activity of Triterpenes HE Shi-nenga，ZHANG Qinga，TANG Zhen-yuanb，XIE Yun-fenga，QIU Lia，XIE Ji-zhao*a (a. College of Pharmacy, b. Higher vocational college, Guangxi Medical University, Nanning 530021, China)
Abstract: Triterpenes are widely found in natural products and are abundant in content. They are one of the main active components of many medicinal plants. Studies on triterpenes have been started as early as the 1930s, which are favored by researchers because of their remarkable biological activity and extensive pharmacological effects. In recent years, the synthesis of triterpenoids and their derivatives has attracted much attention. Structural modification on triterpenes mainly begins with tetracyclic and pentacyclic triterpenes. The modification sites of tetracyclic triterpenes focus on the C-2, C-3 position of ring-A and the side chain of ring-D, mainly introducing hydroxyl, ester or nitrogen-containing groups. Modifications of pentacyclic triterpenes are C-2, C-3 position of ring-A and C-28 position, including esterification, amidation and introduction of nitrogen-containing structure. Besides, some unusual modification sites also show an important effect on biological activity. The progress of structural modification and changes in biological activity of triterpenes and their derivatives were reviewed, in order to provide references for the synthesis, modification and further development and utilization of triterpenes.
Key words: tetracyclic triterpenes; pentacyclic triterpenes; structural modification; biological activity; derivative
引用本文：何诗能，张清，谭珍媛，等. 三萜类化合物结构修饰及活性研究进展[J]. 化学试剂, 2023, 45(5): 41-50。
8-羟基喹啉衍生物镍(II)配合物的合成、晶体结构、抗肿瘤活性及其与BSA作用研究
袁涛1,2，覃姣兰*1,2，黄如川2，姚鹏飞1,2，范歆晨2，谢亚茹1,2
(1.广西城市水环境重点实验室; 2.百色学院，广西 百色 533000)
摘要：以8-羟基喹啉-2-甲醛和2-肼基-4,6-二甲基嘧啶缩合得到席夫碱配体L，配体L与NiCl2•6H2O反应得到配合物[Ni(L)Cl2](简称L-Ni)，X-单晶衍射表明配合物L-Ni属于三斜晶系，空间群P-1。MTT实验表明，配合物L-Ni对肿瘤细胞MGC-803、NCI-H460、T-24、Skov-3的生长均有抑制作用，对T-24的抑制作用最强，IC50=（16.65±0.18）µmol/L，细胞毒性大于顺铂。从荧光光谱结果看，配合物L-Ni能使牛血清白蛋白(BSA)的荧光发生静态猝灭，两者间主要作用力为氢键和范德华力。配合物L-Ni与BSA间有一个结合位点，紫外-可见光谱、同步荧光光谱及位点竞争实验表明，配合物L-Ni与BSA亚结构域ⅡA的位点Ⅰ结合，使BSA微环境极性减小，而疏水性增加，推测配合物L-Ni使BSA的二级结构发生了改变。
关键词：镍配合物；抗肿瘤；光谱研究；静态猝灭；相互作用
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0028
Synthesis, Crystal Structure, Antitumor Activity and Interaction with BSA of Nickel (II) Complex with 8-Hydroxyquinoline Derivative YUAN Tao1,2, QIN Jiao-lan*1,2, HUANG Ru-chuan2, YAO Peng-fei1,2, FAN Xin-chen2, XIE Ya-ru1,2 (1. Guangxi Key Laboratory of Urban Water Environment; 2. Baise University, Baise 533000，Guangxi, China)
Abstract：The schiff base ligand L was synthesized by condensation of 8-hydroxyquinoline-2-formaldehyde and 2-hydrazino-4,6-dimethylpyrimidine, L reacted with NiCl2•6H2O to obtain the complex [Ni(L)Cl2] (L-Ni), X-single crystal diffraction showed that L-Ni belongs to the triclinic system, and the spatial group P-1. MTT test showed that L-Ni inhibited the growth of tumor cells MGC-803, NCI-H460, T-24 and Skov-3, it has the strongest inhibition on T-24, IC50=（16.65 ± 0.18）µmol/L and its cytotoxicity is greater than that of cisplatin. According to the fluorescence spectroscopy results, L-Ni can quench the fluorescence of bovine serum albumin (BSA) statically, and the main binding forces between them are hydrogen bonding and Van der Waals force.There is a binding site between L-Ni and BSA, the Uv-vis spectra, synchronous fluorescence spectra and site tests showed that L-Ni binds to site I of BSA subdomain IIA, and caused the polarity of BSA microenvironment decrease, while the hydrophobicity increased, which inferred that L-Ni changes the secondary structure of BSA.
Key words：Nickel complex; Antitumor; Spectral studies; Static quenching; Interaction
引用本文：袁涛，覃姣兰，黄如川，等. 8-羟基喹啉衍生物镍(II)配合物的合成、晶体结构、抗肿瘤活性及其与BSA作用研究[J]. 化学试剂, 2023, 45(5): 51-58。
2-苯基苯并咪唑诱导的线粒体功能障碍
焦元红*1a,1b，张晓卉1a，徐娟1a，潘凌立2
（1. 湖北理工学院 a.化学与化工学院，b. 矿区环境污染控制与修复湖北省重点实验室，湖北 黄石 435003；2. 鄂东医疗集团黄石市中心医院病案统计科，湖北 黄石 435002）
摘要：苯并咪唑及其衍生物因其优异的药用和药理特性而受到广泛关注。研究表明，苯并咪唑具有很好的抗癌活性。然而到目前为止，苯并咪唑与线粒体相互作用的机制还没有很好地阐明。以大鼠离体线粒体为研究对象，系统研究了2-苯基苯并咪唑对离体线粒体功能和结构的影响。实验研究表明，2-苯基苯并咪唑对线粒体肿胀、线粒体内膜对H+和K+的渗透性、线粒体膜电势、膜流动性、线粒体的呼吸产生强烈的影响。线粒体肿胀、跨膜电位下降和膜流动性下降是2-苯基苯并咪唑诱导线粒体MPTP打开的重要因素。这些发现有助于更多的理解2-苯基苯并咪唑在亚细胞水平上的活性，对线粒体靶向药物的研究具有重要意义，将有助于提高线粒体靶向抗癌药物的活性和选择性。
关键词：2-苯基苯并咪唑；线粒体；线粒体膜渗透性转换；膜流动性；膜电势
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0023
Dysfunction in Mitochondria Induced by 2-phenyl Benzimidazole JIAO Yuan-hong*1a,1b, ZHANG Xiao-hui1a, XU Juan1a, PAN Ling-li2 (1. Hubei Polytechnic University a. College of Chemistry and Chemical Engineering; b. Hubei Key Laboratory of Mine Environmental Pollution Control & Remediation, Huangshi 435003, China; 2. Medical Record Statistics Department,Huangshi Center Hospital, Edong Healthcare Group, Huangshi 435002, China)
Abstract: Benzomidazole and its derivatives have attracted the much attention for their remarkable medicinal and pharmacological properties. Multiple studies have shown that benzimidazole has very prominent anti-cancer activity. Until now, however, the mechanism of how benzimidazole interacts with mitochondria has not been well elucidated. Taking rat isolated mitochondria as the research object, the effect of 2-phenylbenzimidazole on the biological function and activity of isolated mitochondria was systematically studied. Through experimental studies, we found that 2-phenylbenzimidazole has strong effects on mitochondrial swelling, mitochondrial membrane permeability to H+ and K+, mitochondrial membrane potential, membrane fluidity. Mitochondrial swelling, decreased transmembrane potential and decreased membrane fluidity are important factors for 2-phenylbenzimidazole-induced mitochondrial MPTP opening. These findings help to understand more about the activity of 2-phenylbenzimidazole at the subcellular level, which has great significance for the research of mitochondrial targeting drugs, and will help to improve the activity and selectivity of mitochondrial-targeted anticancer drugs.
Key words: 2-phenylbenzimidazole; mitochondrial; mitochondrial membrance permeability transition; membrane fluidity; membrane potential
引用本文：焦元红, 张晓卉, 徐娟, 等. 2-苯基苯并咪唑诱导的线粒体功能障碍[J]. 化学试剂, 2023, 44（5）：59-65.
【功能材料】
生物炭对废水中铜离子吸附的研究进展：改性方法与吸附机制
刘丽1，范世锁*2，梅杨璐2
（1. 阜阳师范大学 物理与电子工程学院，安徽 阜阳 236037；2. 安徽农业大学 资源与环境学院，安徽 合肥 230036）
摘要：废水中的重金属铜离子（Cu(II)）会污染水体生态环境，并会通过食物链对人体健康造成潜在危害。生物炭可作为废水中Cu(II)去除的有效吸附剂。然而，原状生物炭对Cu(II)的吸附量有限，需要对生物炭进行定向改性以提升其去除效果。以废水中的Cu(II)为对象，重点论述生物炭的改性方法和吸附机制。结果表明：生物炭的主要改性方法包括：化学改性（酸、碱、高分子聚合物改性）、物理改性（球磨和气体活化）、金属改性（铁、锰改性）、矿物质改性和高分子聚合物改性等。改性方法对Cu(II)去除效果的次序是：纳米羟基磷灰石改性＞含氨基有机酸改性＞锰改性＞铁改性＞碱改性。生物炭吸附Cu(II)的主要机制包括孔隙扩散、静电作用、沉淀作用、配位作用、阳离子-π机制、离子交换和还原作用，具体的主导机制取决于生物炭的物化性质和溶液的性质。将来的研究方向包括：采取更为有效的改性方法提高对废水中痕量Cu(II)的去除效果；利用先进的仪器和模型计算揭示微观机制；开展动态吸附柱或固定床试验。
关键词：生物炭；铜离子；改性方法；吸附行为；机制
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.2022.0643
Copper Ion Removal from Wastewater by Biochar: Modification Method and Adsorption Mechanism LIU Li1, FAN Shi-suo*2, MEI Yang-lu2 (1. School of Resources and Environment, Anhui agricultural university, Anhui Hefei 230036, China; 2. School of Physics and Electronic Engineering, Fuyang Normal University, Fuyang, 236037, China)
Abstract：Excessive copper ions in wastewater threaten the water ecological environment and cause potential harm to human health through the food chain. Biochar has been confirmed to be an effective adsorbent for Cu ion removal from wastewater. However, the adsorption capacity of the pristine biochar was limited. Modification can improve the adsorption amount of biochar. The modification method and adsorption mechanism of copper ions on biochars were summarized. The results showed that the main modification methods include chemical modification (acid and alkaline activation), physical modification (ball-milling and gas activation), metal modification (Fe and Mn), mineral modification, and high-molecular polymer modification. The order of removal effect of the modified methods on copper ions is as follows: nano-hydroxyapatite>amino-containing organic acid modification >manganese modification>iron modified>alkaline modification. The adsorption mechanisms of copper ion removal by biochar include pore-filling effect, electrostatic action, precipitation action, complexation, cation exchange, ion exchange and reduction. Specific dominant mechanisms highly depended on the physicochemical properties of biochar and experimental conditions. Future research should focus on precise modification methods to enhance the adsorption capacity of copper ions, reveal microscopic mechanisms through advanced instruments combined with theoretical calculations, and perform dynamic adsorption columns or fixed bed experiments.
Key words: biochar; Cu ions; modification approach; adsorption behavior; mechanisms
引用本文：刘丽，范世锁，梅杨璐. 生物炭对废水中铜离子吸附的研究进展：改性方法与吸附机制[J]. 化学试剂, 2023, 45(5): 66-76。
基于AMD回收的生物炭修饰LDHs降解土霉素研究
王新泉1，王进*1，邓锐1，许庆升1，揣新2，张凯2，岳正波1
(1. 合肥工业大学 资源与环境工程学院 安徽省工业废水处理与资源化工程研究中心，安徽 合肥 230000；2. 安徽省马钢矿业资源集团南山矿业有限公司，安徽 马鞍山 243000)
摘要：采用共沉淀法模拟酸性矿山废水（Acid Mine Drainage，AMD）的中和处理过程，利用生物炭优化调控中和过程，负载修饰获得层状双氢氧化物-生物炭复合材料（RLDH@BC），用于活化过一硫酸盐（PMS）降解水中土霉素（OTC）。各项表征结果证明，该方法可成功从AMD中回收RLDH@BC。降解实验表明，RLDH@BC可在广泛的pH范围（3～11）高效活化PMS降解OTC，最高去除效率达到88%；共存离子实验表明，NO3-和HCO3-共存条件下OTC的去除率从86.2%分别降至82.3%、82.2%，影响较小；而Cl-和H2PO42-共存时OTC的去除率分别降至76.1%、68.7%，产生一定影响。猝灭实验表明，在RLDH@BC/PMS体系中，自由基和非自由基共同作用，其中自由基占主导作用。经过5个循环后，70 %的OTC在20 min内被去除，说明材料具有良好的循环利用性。该研究对拓展AMD的资源化处置以及抗生素废水的高效修复均具有重大意义。
关键词：层状双氢氧化物；生物炭；过一硫酸盐；土霉素；降解机制。
中图分类号：X703 文献标识码：A 文章编号：0258-3283(2023)05
DOI：10.13822/j.cnki.hxsj.2023.0117
Degradation of Oxytetracycline by Biochar-modified LDHs Based on AMD Recovery WANG Xin-quan1, WANG Jin*1, DENG Rui1, XU Qing-sheng1, CHUAI Xin2, ZHANG Kai2, YUE Zheng-bo1 (1a. School of Resource and Environmental Engineering, 1b. Anhui Province Industrial Wastewater Treatment and Resourcefulness Engineering Research Center, Hefei 230000, China; 2. Anhui Magang Mining Resources Group Nanshan Mining Co, Maanshan 243000, China)
Abstract：The co-precipitation method was used to simulate the neutralization process of acid mine drainage (AMD), and the biochar loading modification was used to obtain the layered double hydroxide-Biochar (RLDH@BC) composite for the activated peroxymonosulfate(PMS) degradation of oxytetracycline (OTC) in water. Various characterization results demonstrated that the method can successfully recover RLDH@BC from AMD. Batch degradation experiments showed that RLDH@BC can efficiently activate PMS to degrade OTC in a wide pH range (3-11), with a maximum removal efficiency of 88%; Coexistence ion experiment showed that the removal of OTC under the coexistence of NO3- and HCO3- decreased from 86.2% to 82.3% and 82.2%, respectively, with less effect, while the removal of OTC under the coexistence of Cl- and H2PO42- decreased to 76.1% and 68.7%, respectively, which had some effect. The bursting experiments showed that in the RLDH@BC/PMS system, free radicals and non-free radicals joined together to degrade OTC, with free radicals dominating. After 5 cycles, 70 % of the OTC was removed within 20 min, indicating that the material has good recyclability. This study has significant implications for expanding the resource utilization of AMD as well as the efficient remediation of antibiotic wastewater.
Key words：layered double hydroxide; biochar; peroxymonosulfate; oxytetracycline; degradation mechanism
引用本文：王新泉，王进，邓锐，等.基于AMD回收的生物炭修饰LDHs降解土霉素研究[J].化学试剂，2023,45（5）:77-84.
响应曲面法优化茶渣生物质炭对土壤氮磷吸附
钱婧1，蔡青松1，黄显怀*1，周肖瑜2，刘英超1，赵金金1
（1. 安徽建筑大学 a. 环境与能源工程学院；b. 环境污染控制与废弃物资源化利用安徽省重点实验室，安徽 合肥 230601；2. 湖州市植保检疫与耕肥管理站，浙江 湖州 313000）
摘要：为了实现茶渣高效资源化利用，将400 ℃热解制备的茶渣生物质炭（TD400）添加至土壤中，探究其对土壤中氮、磷等养分元素的固持的影响。通过响应曲面分析法Box-Behnken 实验设计原理分析生物质炭添加比、环境pH和反应温度对铵态氮和磷酸盐土壤吸附率的影响。通过模型优化铵态氮最佳吸附条件为生物质炭添加比1.0%、pH 10、反应温度为 15℃；磷酸盐为：生物质炭添加配比为1.0%、pH 10、溶液反应温度为35 ℃。各因素对铵态氮和磷酸盐吸附率的影响大小顺序为：添加土壤配比＞溶液反应温度＞溶液pH，最佳吸附条件下铵态氮和磷酸盐吸附率分别为60.74%及82.59%，与预测值63.25%和81.54%基本吻合。这表明茶渣生物炭可有效固持土壤或吸附水体中的氮磷，为茶渣资源化利用提供了新思路，研究成果具有一定的理论价值和指导意义。
关键词：茶渣生物质炭；吸附；响应曲面法；铵态氮；磷酸盐
中图分类号：S156.2 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0062
Optimization of Soil Adsorption of Nitrogen and Phosphorus with Tea Residue Biochar by Response Surface Methodology QIAN Jing1, CAI Qing-song1, HUANG Xian-huai*1, ZHOU Xiao-yu2, LIU Ying-chao1, ZHAO Jin-jin1 (1a. School of Environment and Energy Engineering, b. Anhui Provincial Key of Environmental Pollution Control and Resource Reuse, Anhui Jianzhu University,Hefei 230601, China; 2. Plant Protection & Quarantine and Tillage & Fertilizer Management Station of Huzhou, Huzhou 313000, China)
Abstract: A biochar prepared by pyrolysing the tea residue at 400 ℃ (TD400) was added into a tea garden soil in order to efficiently utilize the tea residue. The influence of TD400 on soil immobilization of nitrogen and phosphorus were studied. The effects of biochar addition ratio, environment pH and temperature on the soil adsorption efficiency of ammonium nitrogen and phosphate were analyzed based on the Box-Behnken experimental design principle in the response surface analysis method. The best adsorption condition for ammonium nitrogen was 1.0% TD400 addition, pH 10, and 15 ℃. The optimal condition for phosphate adsorption is 1.0% TD400 addition, pH 10, and 35 ℃. The influence of those three factors on soil ammonium nitrogen and phosphate adsorption efficiency varies: biochar addition ratio > environment temperature > pH. The best adsorption efficiency of ammonium nitrogen and phosphate were 60.74% and 82.59% respectively under the optimal adsorption condition, which were basically consistent with our predicted values, 63.25% and 81.54%. The results showed the tea residue biochar could effectively immobilization soil nutrients. This study provided a new idea for the utilization of tea residues and have certain theoretical value and practice significance.
Key words: tea residue biochar; adsorption; response surface methodology; ammonium nitrogen; phosphate
引用本文：钱婧, 蔡青松，黄显怀，等. 响应曲面法优化茶渣生物质炭对土壤氮磷吸附[J]. 化学试剂, 2023, 45（5）：85-92.
喹啉羧酸酯与水合肼的反应性凝胶及专一性识别
靳清贤，张广慧，刘冬，朱性堃，靳清艳，赵文阁，肖元化，方少明*
（郑州轻工业大学 材料与化学工程学院，河南 郑州 450000）
摘要：合成了一类喹啉羧酸酯类及其酰肼类衍生物，结构经HNMR、MS、熔点表征确认。发现了喹啉羧酸酯醇溶液与水合肼反应成胶的特性，对形成的凝胶进行SEM结构分析，发现其主要形成了长纤维结构。考察了溶液浓度、水合肼用量等因素对成胶性的影响。同时研究了喹啉羧酸酯与氨水、甲胺、苯肼、甲基肼的成胶性，发现喹啉羧酸酯仅对水合肼表现出反应成胶性，而对氨水、甲胺、苯肼、甲基肼则保持溶液状态。喹啉羧酸酯与水合肼的快速、专一、定量地形成一种反应性小分子凝胶这一特性，有望为水合肼的定性定量分析提供一种新思路。
关键词：喹啉羧酸酯；酰肼；水合肼；凝胶；识别；反应性小分子凝胶
中图分类号：O626 文献标识码：A 文章编号： 0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0903
Reactive Organogels and Specificity Recognition of Quinoline Carboxylate and Hydrazine Hydrate JIN Qing-xian, ZHANG Guang-hui, LIU Dong, ZHU Xing-kun, JIN Qing-yan, ZHAO Wen-ge, XIAO Yuan-hua, FANG Shao-ming* (School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000, China)
Abstract：A class of quinoline carboxylic acid esters and their hydrazide derivatives were synthesized, and their structures were confirmed by HNMR, MS, and melting point characterization. The reaction characteritics of quinoline carboxylate alcohol solution with hydrazine hydrate to form gels were found, and SEM structural analysis of the formed gels revealed that they mainly formed long fiber structures. The effects of solution concentration and the amount of hydrazine hydrate on gel forming properties were investigated. The gel-forming properties of quinoline carboxylic acid esters with ammonia, methylamine, phenyl hydrazine and methylhydrazine were also investigated, and it was found that quinoline carboxylic acid esters showed reactive gel forming properties only for hydrazine hydrate, while they remained in solution for ammonia, methylamine, phenyl hydrazine and methylhydrazine. The property that quinoline carboxylic acid esters form a small reactive molecule gel with hydrazine hydrate rapidly, specifically and quantitatively, is expected to provide a new idea for qualitative and quantitative analysis of hydrazine hydrate.
Key words：quinoline carboxylate ester; carbohydrazide; hydrazine hydrate; gel; recognition; Reactive organogels
引用本文：靳清贤, 张广慧, 刘冬, 等. 喹啉羧酸酯与水合肼的反应性凝胶及专一性识别[J]. 化学试剂, 2023, 44（5）：93-97.
【分离提取技术】
微波协同离子液体[BMIm]Br提取茶皂素
喻冬秀*1,2，叶旅彬1，王秋怡1，黄淑莉1，钟建军1
（1.电子科技大学 中山学院 材料与食品学院，广东 中山 528402；2.暨南大学 化学与材料学院， 广东 广州 510632）
摘要：采用微波协同离子液体[BMIm]Br对茶油饼中茶皂素进行提取，利用单因素实验及Box-Behnken响应面法对离子液体种类、浓度、固液比、提取温度、提取时间和微波功率等因素进行优化，得到基于5.00 g初料的最优条件为：离子液体[BMIm]Br浓度为1.13 mol/L、料液比1∶10（g/g）、微波功率300 W、提取时间13 min、提取温度68 ℃，得率为（15.01±0.16）%，提取率为80.57%，纯度为83.06%。显色反应和FTIR分析显示微波协同离子液体提取的茶皂素具有茶皂素的结构特征，接触角结果显示本研究方法所提取的茶皂素润湿性优于市售茶皂素(>95%)，临界胶束浓度CMC为0.44 g/L，略低于市售茶皂素(>95%)的0.47 g/L。
关键词：离子液体；微波技术；茶皂素；表面活性
中图分类号：O628.2 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0825
Microwave Assisted Extraction of Tea Saponin by Ionic Liquid [BMIm]Br YU Dong-xiu *1,2, YE Lv-bin1, WANG Qiu-yi1, HUANG Shu-li1, ZHONG Jian-jun1 (1.College of Material and Food, University of Electronic Science and Technology, Zhongshan Institute, Zhongshan 528402; 2.College of Chemistry and Materials Science, Jinan University, Guangzhou 510632,China)
Abstract: Tea saponin was extracted from camellia oil bran by microwave synergistic ionic liquid [BMIm]Br. The type and concentration of ionic liquid, solid-liquid ratio, extraction temperature, extraction time and microwave power were optimized by single factor experiment and Box-Behnken response surface method. The results showed that the optimal extraction conditions based on 5.00 g Initial material were following the concentration of ionic liquid [BMIm]Br of 1.13 mol/L, solid-liquid ratio of 1∶10（g/g）, the microwave power of 300 W, extraction time of 13 min, extraction temperature of 68 °C. Under these conditions, the yield of tea saponin was 15.01±0.16% , the extraction rate was 80.57% and the purity of tea saponin was 83.06% were achieved. Color reaction and FTIR analysis showed that it has the structural characteristics of tea saponin which was extracted by microwave synergistic ionic liquid was complete, and the contact angle results showed that its wettability of self-made tea saponin was better than that of commercial tea saponin (>95%), and its CMC (Critical micelle concentration) was 0.44 g/L, slightly lower than 0.47 g/L of commercially available tea saponin (>95%).
Key words: ionic liquid; microwave technique; tea saponin; surface activity
引用本文：喻冬秀，叶旅彬，王秋怡，等. 微波协同离子液体[BMIm]Br提取茶皂素[J]. 化学试剂, 2023, 45(5): 98-105。
超声-酶法辅助提取青叶胆多酚工艺优化及抗氧化性研究
李汝艳，杨申明*，张琪麟，许斌彬，王振吉
（楚雄师范学院 资源环境与化学学院，云南 楚雄 675000）
摘要：以青叶胆为材料，采用超声-酶法辅助提取青叶胆多酚（Swertia leducii Franch. polyphenols，SLP）并研究其抗氧化性，为开发利用SLP提供参考依据。在考察单因素试验基础上，利用响应面试验优化超声-酶法辅助提取SLP工艺条件，并通过测定SLP对DPPH自由基（DPPH·）、羟自由基（·OH）的清除率和总抗氧化能力来评价其多酚抗氧化性。结果表明，SLP最佳提取条件为：液料比29:1（mL/g）、乙醇体积分数60%、超声温度32 ℃、超声时间29 min、超声功率300 W、纤维素酶用量7.0%（以青叶胆干粉质量为基准，下同），此时，SLP提取量为（16.38±0.21） mg/g，与模型预测值（16.42 mg/g）接近；在质量浓度为0.007 mg/mL时，SLP对DPPH·清除能力稍弱于药维生素C清除能力，SLP对·OH清除能力和总抗氧化能力均明显强于药维生素C。超声-酶法辅助是一种有效提取SLP的提取方法；SLP具有较强的抗氧化活性，是一种具有开发潜力的抗氧化剂。
关键词：青叶胆；多酚；超声-酶法辅助提取；响应面试验；抗氧化性
中图分类号：O629.9 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0010
Optimization and Antioxidant Activity of Polyphenols from Swertia leducii Franch. by Using Ultrasonic-Enzyme-Assisted Extraction Technology LI Ru-yan, YANG Shen-ming*, ZhANG Qi-lin, XU Bin-bin, WANG Zhen-ji (Department of Resources, Environment and Chemistry, Chuxiong Normal University Chuxiong, 675000, China)
Abstract: Polyphenols from Swertia leducii Franch. (SLP) were extracted by using ultrasonic-enzyme-assisted extraction technology, and investigation of antioxidant properties of SLP was performed, which provides reference for the development and utilization of SLP. On the basis of single factor test, response surface test was used to optimize the ultrasonic-enzyme-assisted extraction of SLP, and the antioxidant activity of polyphenols was evaluated by measuring the clearance rate and total antioxidant capacity of SLP against DPPH free radical and hydroxyl free radical. The results showed that the optimal extraction conditions for SLP were liquid-to-material ratio of 29:1 (mL/g), ethanol volume fraction of 60%, ultrasound temperature of 32℃, ultrasound time of 29 min, ultrasound power of 300 W, cellulase usage of 7.0% (based on the mass of S. leducii dry powder, the same below), and the extraction amount of SLP was (16.38±0.21) mg/g under the above conditions, which was approximate to the model-predicted value (16.42 mg/g). At a mass concentration of 0.007 mg/mL, the DPPH·scavenging ability of SLP was slightly weaker than that of pharmaceutical vitamin C, SLP exhibited significantly stronger effects on both·OH scavenging capacity and total antioxidant capacity than that of the medicine vitamin C. Ultrasonic-enzyme-assisted extraction is an effective method for SLP extraction. SLP has strong antioxidant activity and is a potential antioxidant.
Key words: Swertia leducii Franch.; polyphenols; ultrasonic-enzyme-assisted extraction; response surface test; antioxidant properties
引用本文: 李汝艳, 杨申明, 张琪麟, 等. 超声-酶法辅助提取青叶胆多酚工艺优化及抗氧化性研究[J]. 化学试剂, 2023, 45（5）：106-112.
【电化学和新能源】
Ni/CrN高效电催化剂的制备及其析氢催化性能
胡骏1,3，梁书芹2，尹宏峰*3
（1. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211；2. 德州学院 化学化工学院，山东 德州 253023；3. 中国科学院宁波材料技术与工程研究所，浙江 宁波 315201）
摘要：氢能是一种具有高能量密度的清洁能源，如何有效的开发绿氢技术是当前社会首要解决的问题，而研发高效稳定的电解水产氢技术的电催化剂是一种可行性的方式，对促进氢能经济的发展具有重要的意义。通过水热-高温热解两步法合成了一种氮化铬支撑镍纳米颗粒的催化剂（Ni/CrN）。利用XRD、XPS、SEM以及TEM等测试手段对催化剂的形貌及结构进行表征，并在碱性环境下对催化剂进行电催化析氢性能的研究。结果表明，Ni/CrN形成了具有珊瑚状的微观结构，优化了电子结构，并且表现出了优异的析氢反应（HER）催化性能，在10 mA/cm2的电流密度下，Ni/CrN催化剂仅有66 mV的过电位和47 mV/dec的Tafel斜率，十分接近商业的Pt/C催化剂的析氢性能。在10 mA/cm2的电流密度的循环稳定性测试中，Ni/CrN表现出比商业Pt/C电极更优越的催化稳定性。
关键词：氢能；析氢反应；过渡金属氮化物；镍；电催化剂
中图分类号：O65 文献标识码：A 文章编号：2023.0026
DOI：10.13822/j.cnki.hxsj.2023.0026
Preparation of Ni/CrN High-Efficiency Electrocatalyst and its Catalytic Performance in Hydrogen Evolution Reaction HU Jun1,3, LIANG Shu-qin2, YIN Hong-feng*3 (1. College of Material Science end Chemical Engineering, Ningbo University, Ningbo 315211, China; 2. College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China; 3. Ningbo Institute of Materials Technology & Engineering, Chinese Academy of sciences, Ningbo 315201, China)
Abstract：Hydrogen energy is a kind of clean energy with a high energy density. It is a primary problem that how to effectively develop green hydrogen technology in the current society. This is a feasible method to study efficient and stable electrocatalysts, which is of great significance to promote the development of hydrogen economy. Nickel-supported chromium nitride catalyst (Ni/CrN) was synthesized by a two-step hydrothermal-ammoniolysis method. The morphology and structure of Ni/CrN were confirmed by XRD, XPS, SEM and TEM, respectively. The hydrogen evolution performance of Ni/CrN was studied in alkaline environments. The results show that the HER overpotential of Ni/CrN catalyst was 66 mV and the Tafel slope is only 47 mV/dec at the current density of 10 mA/cm2, which is very close to the performance of the commercial Pt/C catalyst. In the cycle stability test of current density of 10 mA/cm2, Ni/CrN showed less voltage drop than commercial Pt/C electrodes, showing excellent stability.
Key words：hydrogen energy; hydrogen evolution reaction; transition metal nitrides; nickel; electrocatal
引用本文：胡骏, 梁书芹, 尹宏峰. Ni/CrN高效电催化剂的制备及其析氢催化性能[J]. 化学试剂, 2023，45（5）：113-119.
锂离子电池硅基阳极预锂化研究进展
杨井玉，侯果林，静若盈，荣峻峰*
（中石化石油化工科学研究院有限公司，北京 100083）
摘要：硅基阳极材料具有超高的理论比容量，是替代石墨类材料、提高锂离子电池能量密度的有效途径。但与石墨类材料相比，硅基阳极材料在首次嵌锂过程中，会大量消耗来自正极的锂离子，造成活性锂损失，形成较大的初始不可逆容量，影响材料的首次库伦效率，严重降低了锂离子电池的能量密度。预锂化技术，通过使电极材料接触额外的锂源，可以补偿锂离子电池在首次循环过程中造成的活性锂损失，是目前提高锂离子电池首次库伦效率的最有效手段，可使锂离子电池获得更高的能量密度和更好的循环性能。对当前主要的预锂化手段进行了概述，总结了各种预锂化技术的优缺点，并提出预锂化技术未来面临的挑战，为预锂化策略的实际性应用提供方向。
关键词：锂离子电池；预锂化；阳极；硅；氧化亚硅
中图分类号：TM912 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0920
Research Progress on Pre-Lithiation of Silicon-Based Anode for Lithium-ion Batteries YANG Jing-yu, HOU Guo-lin, Jing Ruo-ying, RONG Jun-feng* (Sinopec Research Institute of Petroleum Processing Co., Ltd, Beijing 100083, China)
Abstract: Silicon-based anode materials have ultra-high theoretical specific capacity, which is an effective way to replace graphite materials and improve the energy density of lithium-ion batteries. However, compared with graphite materials, silicon-based anode materials will consume a large amount of lithium ions from positive electrodes in the first lithium intercalation process, resulting in active lithium loss, forming a larger initial irreversible capacity, affecting the first Coulomb efficiency of the materials, and seriously reducing the energy density of lithium-ion batteries. The pre-lithiation technology, which can compensate for the active lithium loss caused by the first cycle of lithium-ion batteries by making the electrode material contact with additional lithium sources, is the most effective means to improve the first Coulomb efficiency of lithium-ion batteries at present, which can make lithium-ion batteries obtain higher energy density and better cycle performance. This review summarizes the main pre-lithiation methods at present, summarizes the advantages and disadvantages of various pre-lithiation technologies, and puts forward the challenges faced by pre-lithiation technology in the future, which provides a direction for the practical application of the pre-lithiation strategy.
Key words: lithium-ion batteries; prelithiation; anode; Si; SiO
引用本文：杨井玉, 侯果林, 静若盈, 等. 锂离子电池硅基阳极预锂化研究进展[J]. 化学试剂, 2023, 45（5）：120-129.
均苯四酸钴铁MOFs衍生材料的制备及其锂离子电池性能研究
耿庆帅，王丽英*，侯亚平
（内蒙古工业大学 化工学院，内蒙古 呼和浩特 010051）
摘要：利用均苯四酸、硝酸钴、氯化铁和活性炭，采用一步水热法制备双金属钴铁金属有机框架（CoFe-MOFs-C），通过在氩气条件下以5 ℃/min的升温速度升到500 ℃，保温2 h，自然降温后获得碳包覆金属氧化物（M-CoFe-C），并通过红外波谱分析、XRD、扫描电镜、XPS和拉曼光谱等分析手段进行了表征。该复合材料是碳紧紧包覆在钴铁氧化物的外层，作为锂离子负极材料，碳层提高电子在电极表面上的传输速度，并在充放电过程中抑制活性材料的体积膨胀。原位构造的包覆碳层，使复合物具有良好的循环稳定性。研究表明，在200 mA/g的电流密度下，第100个循环时的可逆容量可达到668.2 mA⸱h/g。
关键词：均苯四酸；金属有机框架；衍生材料；锂离子电池；负极材料
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2022.0901
Preparation of Anode Materials Derived CoFe-MOFs Supported by Pyromellitic Acid and Study on the Performance of Lithium Ions Batteries GENG Qing-shuai, WANG Li-ying*, HOU Ya-ping (School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China)
Abstract: The organic bimetallic cobalt iron metal framework (CoFe-MOFs-C) was prepared by a one-step hydrothermal method using pyromellitic acid, cobalt nitrate, ferric chloride and activated carbon. The metal oxide coated carbon (M-CoFe-C) was obtained by raising the temperature to 500 ℃ at a rate of 5 ℃/min under argon gas conditions, holding for 2 h, naturally cooling, and was characterized by infrared spectroscopy, XRD, scanning electron microscopy, XPS and Raman spectroscopy. The composite material is cobalt iron oxide tightly coated with a layer of carbon. As lithium ion anode material, the carbon layer improves the electron transport speed on the electrode surface, and inhibits the volume expansion of the active material during charging and discharging, so it has good cycle stability. The research shows that at the current density of 200 mA/g, the reversible capacity at the 100th cycle can reach 668.2 mA⸱h/g.
Key words: pyromellitic acid; metal organic framework; derivative materials; lithium ions battery; anode material
引用本文：耿庆帅，王丽英，侯亚平. 均苯四酸钴铁MOFs衍生材料的制备及其锂离子电池性能研究 [J]. 化学试剂，2023，45（5）：130-135.
【化学品与环境】
席夫碱荧光探针的合成及其对三价金属的识别
聂梅1,2，汤静洁1,2，黎鹏1,2，温慈恩3，秦健南1,2，黄冬婷*1,2
（1.广东省科学院生物与医学工程研究所，广东 广州 510316；2.广东省绿色制糖工程技术研究中心，广东 广州 510316；3.广东第二师范学院 生物与食品工程学院，广东 广州 510303）
摘要：Al3+、Cr3+、Fe3+、Ce3+对环境和生物体有重要影响，能同时检测这4种三价金属离子的荧光探针较为少见。以2-氨基蒽和对苯基苯甲醛制备了一种席夫碱类荧光探针I，通过1HNMR、HRMS和元素分析对其结构进行了表征。光谱分析实验结果表明，探针I在四氢呋喃/水（V（THF）∶V（水）＝1∶1）溶液中对三价金属Al3+、Cr3+、Fe3+和Ce3+具有较强荧光响应，有较高选择性和快速响应，且不受其他金属离子或阴离子影响，抗干扰能力强，检测的最适pH范围为5～9。结合高分辨质谱检测、紫外测试和理论计算，证实探针与三价金属的作用机理为：探针与三价金属作用后，分解生成2-氨基蒽，发出荧光。进一步，将荧光探针负载于试纸条，成功实现对三价金属的试纸检测。
关键词：2-氨基蒽；席夫碱；荧光探针；三价金属离子；试纸检测
中图分类号：O621 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0021
Synthesis of a Schiff Base Fluorescent Probe and Its Selective Detection of Trivalent Metallic Ions NIE Mei1,2, TANG Jing-jie1,2, LI Peng 1,2, WEN Ci-en 3，QIN Jian-nan 1,2，HUANG Dong-ting*1,2（1. Institute of Biological and Medical Engineering, Guangdong Academy of Sciences, Guangzhou 510316, Guangdong, China;2. Guangdong Province Engineering Research Center for Green Technology of Sugar Industry, Guangzhou 510316, Guangdong, China;3. College of Biology and Food Engineering, Guangdong University of Education, Guangzhou 510303, Guangdong, China）
Abstract: Al3+、Cr3+、Fe3+、Ce3+ have important effects on the environment and organisms, fluorescent probes that can simultaneously detect these four trivalent metal ions are rare. A fluorescent probe I was synthesized by Schiff base condensation of 2-aminoanthracene with biphenyl-4-carboxaldehyde, which had been carefully characterized by 1HNMR, HRMS and elemental analysis. The experimental results of spectroscopic analysis showed that probe I has a high fluorescence response to trivalent metals Al3+、Cr3+、Fe3+and Ce3+ in THF/H2O（V（THF）∶V（H2O）＝1∶1）. The probe I was highly selective and rapid response to trivalent ions over other metal ions or anions and had a strong anti-interference ability. The optimum range of probe I was pH 5～9. Based on high resolution mass spectrometry detection, ultraviolet detection and theoretical calculation results, probe I proposed decomposition into 2-aminoanthracene and emit fluorescence after interaction with the trivalent metal. Further, the fluorescent probe I was loaded on the test strip to successfully detect the trivalent metal.
Key words: 2-aminoanthracene; Schiff base; fluorescent probe; trivalent ions; strips test
引用本文：聂梅，汤静洁，黎鹏，等. 席夫碱荧光探针的合成及其对三价金属的识别[J]. 化学试剂, 2023, 45(5): 136-141..
磁性聚吡咯基材料制备及对印染废水中Cr(VI) 吸附特性研究
陶冶*1，周文涛2
(1. 重庆财经职业学院，重庆 402100；2.重庆大学 化学化工学院，重庆 400044)
摘要：首先通过原位氧化聚合法制备富氮聚合物（PPy），然后以PPy前体和磁性金属粉末在高温条件下成功制备出两性吸附剂 CN@Co3Fe7。利用扫描电镜（SEM）、红外光谱（IR）、X射线衍射仪(XRD)和透射电镜（TEM）等多种手段对合成吸附材料进行了形貌和结构表征，并系统考察了其对纺织印染废水中Cr(VI)的吸附性能。试验结果表明：制备出的纳米吸附材料呈六方块结构，粒径为150 nm，饱和磁化强度约49.1 emu /g，对Cr(VI)具有良好的吸附能力，在吸附剂用量=4 mg/L、pH=1.7、Cr(VI)初始浓度=200 mg/L的条件下吸附1h对Cr(VI)去除率可达99.48%，3次再生后去除率仍可维持在83.41%。吸附动力学规律遵循准一级动力学模型，而吸附等温线符合Freundlich 等温吸附模型，说明吸附是一个多层不均匀吸附。
关键词：吸附；磁性聚吡咯基；热力学；吸附动力学；Cr(VI)
中图分类号：TQ352 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0037
Preparation of Magnetic Polypyrrole Based Material and Its Adsorption Characteristics for Cr(VI) in Textile Wastewater TAO Ye1, ZHOU Wen-tao2 (1. Chongqing College of Finance and Economics, Yongchuan Chongqing 402100, China; 2. School of Chemistry and Chemical Engineering, Chongqing University, Shapingba Chongqing 40044, China)
Abstract：Nitrogen-rich polymer (PPy) was firstly prepared by in-situ oxidation polymerization and then amphoteric adsorbent CN@Co3Fe7 was successfully prepared from PPy precursor and magnetic metal powder. Morphology and structure of the synthesized adsorbent were characterized by scanning electron microscopy (SEM), infrared spectroscopy (IR), X-ray diffractometer (XRD) and transmission electron microscope(TEM). Its adsorption properties for Cr(VI) in textile printing and dyeing wastewater were systematically investigated. The test results showed that the prepared nano adsorbent had a hexagonal structure with a particle size of about 150 nm. Saturated magnetization was about 49.1 emu/g. It had good adsorption capacity for Cr(VI). Removal rate of Cr(VI) could reach 99.48% after 1h adsorption under the conditions that the amount of adsorbent=4 mg/L, pH=1.7 and the initial concentration of Cr(VI)=200 mg/L, and the removal rate could still be maintained at 83.41% after three regenerations. The adsorption kinetics followed the quasi first order kinetic model. The adsorption isotherm showed that the adsorption law conforms to the Freundlich isotherm adsorption model, indicating that the adsorption was a multi-layer heterogeneous adsorption.
Key words：adsorption; magnetic polypyrrole group; thermodynamics; adsorption kinetics; Cr(VI)
引用本文：陶冶，周文涛. 磁性聚吡咯基材料制备及对印染废水中Cr(VI) 吸附特性研究[J]. 化学试剂，2023，45（5）：142-147.
己二酸/硫酸掺杂聚苯胺对Cr(Ⅵ)的吸附行为
蔡雨晴1，章东雪1，周娇1，周进康*1，孔垂灿1，李玉驳1,刘应科2
（1.贵州师范学院 化学与材料学院，贵州 贵阳 550018；2. 贵阳神迪化工有限公司，贵州 贵阳，550018 ）
摘要：为了研究己二酸掺杂聚苯胺对重铬酸钾溶液的吸附行为，以己二酸(AA)、硫酸为混合掺杂剂，采用化学氧化聚合法合成了己二酸/硫酸掺杂聚苯胺(PANI@H/AA)。采用FT-IR、SEM及EDS分析方法对其结构进行了表征，考察了苯胺与己二酸物质的量比、吸附液初始浓度、吸附时间、pH值对Cr(Ⅵ)吸附行为的影响。分析了PANI@H/AA对Cr(Ⅵ)的吸附行为特征。结果表明：n（苯胺）∶n（己二酸）=5∶2时，PANI@H/AA显示出优异的吸附效果，其对Cr(Ⅵ)的吸附行为符合Langmuer单分子层和二级动力学吸附模型。对Cr(Ⅵ)的吸附行为主要是掺杂聚苯胺中的—N+＝正离子以及酸性条件下质子化的亚氨基对HCrO4－、Cr2O72－的静电吸引作用。PANI@H/AA能够对废水中Cr(Ⅵ)进行有效去除，并具有较好的重复使用性能。
关键词：己二酸；掺杂；聚苯胺；吸附；Cr(Ⅵ)
中图分类号：TQ 028.8 文献标志码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0854
Adsorption Behavior of Adipic/sulfuric Acid Doped Polyaniline for Cr(VI) CAI Yu-qing1, ZHANG Dong-xue1, ZHOU jiao1, ZHOU Jin-kang*1, KONG Chui-can1, LI Yu-bo1, LIU Ying-ke2 (1.College of Chemistry and materials, Guizhou Normal University, Guiyang 550018, Guizhou, China; 2.Guiyang Shendi Chemical Co., LTD. Guiyang 550018, Guizhou, China)
Abstract: In order to study the adsorption behavior of adipic acid doped polyaniline on potassium dichromate solution,adipic acid doped polyaniline was prepared by oxidative polymerization using aniline as raw materials, apic acid / sulfuric acid doped polyaniline (PANI@H/AA) was synthesized by chemical oxidation polymerization by using adipic acid (AA) and sulfuric acid as mixed dopants. The Flourier transform infrared spectroscopy (FT-IR)，scanning electron microscope (SEM) and EDS were used to determine that AA was effectively doped on PANI structure was formed. The effects of aniline/adipic acid molar ratio, initial concentration of adsorbent, adsorption time and pH on Cr(VI) adsorption behavior were investigated. The characteristics of the adsorption behavior of adipic acid doped polyaniline (PANI@H/AA) on potassium dichromate solution was investigated, and the relevant mechanism were analyzed. The results showed that when the molar ratio of aniline to adipic acid was 5:2, the PANI@H/AA showed outstanding adsorption effect. The adsorption behavior of Cr(Ⅵ) was consistent with the Langmuer monolayer and second-order kinetic adsorption model. The adsorption behavior of Cr(Ⅵ) was mainly due to the doping of —N += positive ions in polyaniline and the electrostatic attraction of proton-induced imino to HCrO4- and Cr2O72- under acidic conditions. PANI@H/AA can effectively remove Cr(Ⅵ) from wastewater and had a good reuse performance.
Key words: adipic acid; dopeing; polyaniline; adsorption; Cr(Ⅵ)
引用本文：蔡雨晴，章东雪，周娇，等. 己二酸/硫酸掺杂聚苯胺对Cr(Ⅵ)的吸附行为[J]. 化学试剂, 2023, 45(5): 148-154。
【分析与测试】
碳纳米点荧光探针高效检测α-葡萄糖苷酶
赵丹，黄晶晶*，王燕敏，马逍
(洛阳理工学院 环境工程与化学学院，河南 洛阳 471023)
摘要：基于α-葡萄糖苷酶（α-Glu）催化底物2-O-α-D-吡喃葡萄糖基-L-抗坏血酸（AA2G）水解和银纳米粒子（AgNPs）在碳纳米点（CNDs）表面的原位生成过程，建立了一种简单、高效的荧光分析方法用于α-Glu活性的检测。α-Glu催化AA2G水解产生具有强还原性的抗坏血酸（AA）；Ag+通过静电相互作用附着在CNDs表面，并被AA还原在CNDs表面原位生成AgNPs，同时，由于二者之间的荧光共振能量转移效应，CNDs的荧光猝灭；荧光猝灭的程度与α-Glu的活性有关，由此可对α-Glu活性进行定量检测。在最优实验条件下，检测α-Glu的线性范围为0.1～2 U/mL和2.5～6 U/mL，检出限（S/N=3）为0.018 U/mL。常见的蛋白和生物酶对α-Glu检测无明显干扰，该荧光探针的选择性良好，在复杂样品中具有较大的应用潜力，为与α-Glu相关疾病的诊断与治疗提供了理论基础。
关键词：α-葡萄糖苷酶；碳纳米点；荧光探针；银纳米粒子；原位生成
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2023.0029
Efficient Detection of α-glucosidase Activity Based on the Carbon Nanodots Fluorescent Probes ZHAO Dan, HUANG Jing-jing*, WANG Yan-min, MA Xiao (College of Environmental Engineering and Chemistry, Luoyang Institute of Science and Technology, Luoyang 471023，China)
Abstract: By using α-glucosidase (α-Glu)-catalyzed hydrolysis of 2-O-α-D-glucopyranyl-L-ascorbic acid (AA2G) and in-situ growth of silver nanoparticles on the surface of carbon nanodots (CNDs), a simple yet efficient fluorescent probe has been designed for the detection of α-Glu activity. α-Glu can catalyze the hydrolysis of AA2G to produce ascorbic acid (AA) with high reducibility. Silver ions could be attached to the surface of CNDs through electrostatic interaction and could be reduced to AgNPs, which in situ grow on the surface of CNDs. Simultaneously, the fluorescence resonance energy transfer from CNDs (donor) to AgNPs (acceptor) could lead to obvious fluorescence quenching of CNDs and the quenching degree was related to α-Glu activity, and thus α-Glu activity can be quantitatively detected. Under optimized conditions, the developed method showed a good linear relationship in the activity range of 0.1 to 2 and 2.5 to 6 U/mL, and provided an inspiring detection limit as low as 0.018 U/mL. Other proteins and enzymes had no obvious interference with α-Glu detection, indicating good selectivity for α-Glu activity detection, which demonstrates great potential in complex samples. Such an approach can provide a theoretical basis for the diagnosis and treatment of α-Glu-related diseases.
Key words：α-glucosidase; carbon nanodots；fluorescent probe；silver nanoparticles; in-situ growth
引用本文：赵丹，黄晶晶，王燕敏，等. 碳纳米点荧光探针高效检测α-葡萄糖苷酶[J]. 化学试剂, 2023, 45(5 ): 155-161。
正丁醇-盐酸法测定花生红衣中原花青素的方法优化
何晓勇*a,b，王璇a,b，郭楠楠a,b，尚雪可a
（郑州科技学院 a.食品科学与工程学院，b.郑州市食品安全快速检测重点实验室，河南 郑州 450064）
摘要：以花生红衣为原料，以原花青素含量为指标，采用优化后的正丁醇-盐酸法测定花生红衣提取物中原花青素的含量。通过单因素试验确定料液比、烘箱温度、保温时间对原花青素含量的影响。采用响应面软件，以单因素试验为基础，设计三因素三水平的响应面试验，并对试验结果进行分析。结果表明，影响花生红衣中原花青素含量的因素顺序为料液比＞烘箱温度＞保温时间，根据实际试验可行性，优化后的正丁醇-盐酸法的最佳条件分别为料液比1:65（g/mL）、烘箱温度90 ℃、保温时间60 min，在此条件下原花青素的含量达到最高为135.003 mg/g。该方法的加标回收率为97.48% ~ 98.78%，相对标准偏差为0.4% ~ 1.1%。优化后的正丁醇-盐酸法具有较高的准确度和精密度，可为原花青素含量的测定方法优化提供参考。
中图分类号：O657.32;TS207.3 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0869
Optimization of n-Butyl Alcohol-Hydrochloric Acid Method for Determination of Proanthocyanidins in Peanut Testa HE Xiao-yonga,b, WANG Xuana,b, GUO Nan-nana,b, SHANG Xue-kea
(a. College of Food Science and Engineering, b. Zhengzhou City Food Safety Rapid Test Key Laboratory, Zhengzhou University of Science and Technology , Zhengzhou 450064, China)
Abstract: Using peanut red coat as raw material and proanthocyanidin content as index, the content of proanthocyanidins in peanut testa was determined by optimized n-butyl alcohol-hydrochloric acid method. The effects of feed liquid ratio, oven temperature and oven time on the content of procyanidins were determined by a single factor test. Using response surface software, based on single factor, three factor and three level response surface tests were designed, and the test results were analyzed. The results showed that the factors affecting the proanthocyanidins content in peanut testa were material-liquid ratio > oven temperature > holding time. According to the actual test situation, the optimum conditions of the optimized n-butyl alcohol-hydrochloric acid method were material liquid ratio 1:65 (g/mL), oven temperature 90 ℃ and oven time 60 min. Under these conditions, proanthocyanidins reached a maximum content of 135.003 mg/g. The standard addition recovery of this method was 97.48% to 98.78%, and the relative standard deviation was 0.4%～1.1%. The optimized n-butanol-hydrochloric acid method has high accuracy and precision, which can provide reference for the optimization of method of determination procyanidins content.
Key words: peanut testa; procyanidins; n-butyl alcohol-hydrochloric acid method; method optimization
引用本文：何晓勇, 王璇, 郭楠楠, 等. 正丁醇-盐酸法测定花生红衣中原花青素的方法优化[J]. 化学试剂, 2023, 45（5）：162-167.
