化学试剂
2024年46（12）中英文摘要
【特约专题】
治疗性单克隆抗体修饰变异体的液质联用分析技术进展
叶沛均，左成意，刘振虎，廖玉玲，江正瑾，王启钦*
(暨南大学 药学院 药物分析研究中心, 广东 广州 511436)
摘要：治疗性单克隆抗体（mAbs）因具有靶向性高、药效作用强等优点而广泛应用于恶性肿瘤和自身免疫性疾病的高效治疗，成为全球新药研发热点。由于抗体药物自身结构复杂，尤其在生产、储存等过程甚至在病人体内易出现各种修饰变化，如氧化、脱酰胺化、糖基化等，这些修饰不仅会增加mAbs的异质性，还会影响其稳定性和生物活性，因此监测mAbs体内外修饰变化情况，对于药物研发、生产及体内命运动态变化分析意义重大。液质联用技术（LC-MS）通过将液相色谱分离和质谱检测相结合已成为抗体质量研究和临床监测的重要分析手段，而mAbs体内分析的生物样本前处理面临着基质干扰严重以及血药浓度低等分析挑战。系统总结了抗体修饰变异体分析技术涉及的样本前处理过程和LC-MS技术的应用进展。
关键词：单克隆抗体；修饰变异体分析；样品前处理；基于质谱的蛋白质组学策略；液质联用技术
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2024）12-0001-12
DOI：10.13822/j.cnki.hxsj.2024.0410
Advances in LC-MS Analysis of Therapeutic Monoclonal Antibody Modification Variants Ye Pei-jun, Zuo Cheng-yi, Liu Zhen-hu, Liao Yu-ling, Jiang Zheng-jin, Wang Qi-qin*（Institute of Pharmaceutical Analysis, College of Pharmacy, Jinan University, Guangzhou 511436, China）
Abstract：Therapeutic monoclonal antibodies (mAbs) are widely used in the efficient treatment of malignant tumors and autoimmune diseases due to their advantages of high targeting and potent effects, and have become a hotspot for new drug research and development worldwide. Due to the complex structure of antibody drugs, modification variants, such as oxidation, deamidation, glycosylation, etc., easily occur in the process of production, storage, and even in patients, which not only increase the heterogeneity of the mAb, but also affect its stability and bioactivity, so the monitoring of the changes of mAb's in vitro and ex vivo modification is essential for the analysis of the drug research and development, production, and the dynamics of the fate of mAb in vivo analysis. Liquid chromatography-mass spectrometry (LC-MS) has become an important analytical tool for antibody quality research and clinical monitoring by combining liquid chromatography separation and mass spectrometry detection, whereas the pre-treatment of biological samples for in vivo analysis of mAb faces analytical challenges such as severe matrix interferences as well as low blood drug concentrations. This paper systematically summarises the sample pre-treatment process and the progress of the application of LC-MS technology involved in the analysis of antibody modification variants.
【综述与专论】
荧光共价有机框架的设计合成及其研究进展
邱蕙婷，杨杰瑞，孟爽*
（云南师范大学 化学化工学院，云南 昆明 650000）
摘要：共价有机框架（COF）是一种周期性多孔材料，是由在原子级别上通过共价键紧密相连的有机结构单元所构成的。它们比表面大，密度小，结晶度好，结构设计简单。在荧光分析检测领域展现出巨大的应用潜力，由于它在荧光分析检测中的应用潜力科研工作者对其产生兴趣。为此，对COFs的结构和荧光性能之间的关系进行了讨论，重点介绍了近年设计合成高荧光性能的二维COF的研究进展，基于荧光COFs面临设计新的扑拓、实际应用、传感领域等方面的挑战进行了分析，并对未来的发展方向进行了展望。
关键词：共价有机框架；结构；设计合成；高荧光性能；研究进展
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2024）12-0013-09
DOI：10.13822/j.cnki.hxsj.2024.0259
Research Progress in the Design and Synthesis of Fluorescent Covalent Organic Frameworks QIU Hui-ting, YANG Jie-rui, Meng Shuang* (School of Chemistry and Engineering, Yunnan Normal University, Yunnan 650000, China)
Abstract: Covalent organic frameworks (COFs) are periodic porous materials formed by the precise connection of organic structural units at the atomic level through covalent bonds. They have the advantages of good crystallinity, low density, high specific surface area and simple structural design. They show great application potential in the field of fluorescence analysis and detection, and have attracted wide attention of researchers. In this paper, the relationship between the structure and fluorescence properties of COFs is discussed. The research progress in the design and synthesis of two-dimensional COFs with high fluorescence properties in recent years is mainly introduced. The challenges faced by fluorescence-based COFs are analyzed, and the development direction in the future is prospected.
光催化苄位C―H键官能团化研究进展
张艳敏*1，王君2，郭国哲1，赵乐1
（1. 陇东学院 石油化工学院 甘肃省陇东油气资源高效利用重点实验室，甘肃 庆阳 745000；
2. 丽彩甘肃西峰制药有限公司，甘肃 庆阳 745700）
摘要：光催化苄位C―H键官能团化在有机合成中的重要性和潜力日益凸显。这一技术在绿色化学与可持续发展的背景下，成为研究热点。利用光催化技术，能够在温和的反应条件下，高效地向苄位引入各种官能团，为复杂有机分子的合成提供了新的途径。该方法不仅简化了合成步骤，还大大提高了产率，为底物结构带来了更多的多样性。对近几年光催化苄位C―H键官能团化反应的研究进行了全面综述，深入探讨了其在合成中的应用。这一领域的发展，不仅推动了有机合成领域的技术进步，也为环境保护和可持续发展做出了积极贡献。
关键词：苄位；C―H官能团化；光催化；烃基化；羧基化；酰基化
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）12-0022-10
DOI：10.13822/j.cnki.hxsj.2024.0089
Advances in photocatalytic functionalization of benzyl C?H bonds ZHANG Yan-min*1, Wang Jun2, GUO Guo-zhe1, ZHAO Le1 (1. Gansu Key Laboratory of Efficient Utilization of Oil and Gas Resources, College of Petroleum and Chemical Engineering, Longdong University, Qingyang 745000, China; 2. Licai Gansu Xifeng Pharmaceutical Co., Ltd., Qingyang 745700, China)
Abstract：The photocatalytic functional group of the benzyl C-H bond has become a research hotspot under the background of green chemistry and sustainable development because of its increasing significance and potential in the field of organic synthesis. By using photocatalysis, various functional groups can be efficiently introduced into benzyl sites under mild reaction conditions, providing a new way for synthesizing complex organic molecules. This method simplifies the synthesis process, increases the yield, and brings more diversity to the structures of substrates. In this paper, we review the recent research on photocatalytic functional group reactions of benzyl C-H bonds and discuss their applications in synthesis. This field's development has not only promoted technological progress in organic synthesis, but also made a positive contribution to environmental protection and sustainable development.
离子液体在纳米材料制备及形貌调控中的研究进展
姚培*1，胡程紫1，秦建国*2，吴天宇1
(1. 常州工程职业技术学院 化工与制药工程学院，江苏 常州213164；2.上海沃凯生物技术有限公司，上海 201506）
摘要：纳米材料对构建电化学传感器电极材料至关重要。通过纳米材料制备和修饰，提高电极材料在电化学传感器中的应用。离子液体具有独特的性质，在纳米材料制备和形貌调控中发挥着重要的作用。综述了离子液体在Au、Ni、Co、Mn基纳米材料制备和形貌控制中的应用发展，结合离子液体阴阳离子的影响及诱导机制进行讨论。最后对离子液体在纳米材料制备的前景和发展进行了展望。
关键词：离子液体；电极材料；纳米材料；制备；形貌调控
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）12-0032-07
DOI：10.13822/j.cnki.hxsj.2024.0241
Research progress of ionic liquids in the preparation and morphology control of nanomaterials YAO Pei*1, HU Cheng-zi1, QIN Jian-guo*2, WU Tian-yu1 (1. School of chemical and pharmaceutical engineering, Changzhou Vocational Institute of Engineering, Changzhou 213164, China; 2. Shanghai Our ChemBio-Technology Co., Ltd., Shanghai 201506, China)
Abstract： Nanomaterials are very important for the construction of electrode materials for electrochemical sensors. Through the preparation and modification of nanomaterials, the application of electrode materials in electrochemical sensors is improved. Ionic liquids have unique properties and play an important role in the preparation and morphology control of nanomaterials. The application and development of ionic liquids in the preparation and morphology control of Au, Ni, Co and Mn-based nanomaterials were reviewed. The influence and induction mechanism of anions in ionic liquids were discussed. Finally, the prospect and development of ionic liquids in the preparation of nanomaterials are prospected.
纳米Ag@Kanamycin复合材料的制备及抑菌性能研究
陈惠惠1，吴迎花1，汪艳1，胡瑞玲1，吴苗1，王嘉伟1，郭少波*1, 2，季晓晖*1, 2
(1. 陕西理工大学 化学与环境科学学院, 陕西 汉中 723000；2. 陕西省催化基础与应用重点实验室, 陕西 汉中 723000)
摘要：近年来，由于抗生素滥用导致耐药菌的出现，这致使人类健康将受到严重威胁。因此，迫切需要研发出一种新型、高效的抑菌剂。以三氟醋酸银(CF3COOAg)为原材料，通过单液相化学还原法制备纳米银颗粒(Ag NPs)，利用“浸渍法”结合市售抗生素硫酸卡那霉素(Kanamycin)合成了Ag@Kanamycin复合材料。通过TEM、XRD、UV-vis、FT-IR、表面静电势(ESP)等对样品的形貌、晶体结构和键合方式等进行系统化表征。以大肠杆菌(E. coli)、金黄色葡萄球菌(S. aureus)和真菌白色念珠菌(C. albicans)为测试菌，通过最小抑菌浓度(MIC) 、滤纸片扩散法、菌落计数法探究复合材料的协同抑菌性能和抑菌机制。抑菌活性显示，复合材料对3种测试菌的MIC分别为40、20和10 μg/mL。抑菌机制表明，复合材料能够有效改变菌体细胞膜通透性并破坏细胞壁，导致细菌凋亡。
关键词：Ag NPs；Kanamycin；协同抑菌；抑菌性能；抑菌机制
中图分类号：TB333 文献标识码：A 文章编号：0258-3283(2024)12-0039-09
DOI：10.13822/j.cnki.hxsj.2024.0292
Preparation and Bacteriostatic Properties of Ag@Kanamycin Nanocomposites CHEN Hui-hui1, WU Ying-hua1, WANG Yan1, HU Rui-ling1, WU Miao1, WANG Jia-wei1, GUO Shao-bo*1, 2, JI Xiao-hui *1, 2 (1. School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China; 2. Shaanxi Province Key Laboratory of Catalytic Foundation and Application, Hanzhong 723000, China)
Abstract: In recent years, the overuse of antibiotics has led to the emergence of drug-resistant bacteria that pose a serious threat to human health. As a result, there is an urgent need to develop a new and effective bacteriostatic agent. In this paper, silver nanoparticles (Ag NPs) were prepared from silver trifluoroacetate (CF3COOAg) by single-liquid-phase chemical reduction. The synthesis of Ag@Kanamycin composites was achieved using the "impregnation method" in combination with the commercially available antibiotic, kanamycin sulphate (Kanamycin). The samples were systematically characterized by TEM, XRD, UV-vis, FT-IR and surface electrostatic potential (ESP) in terms of their morphology, crystal structure, and bonding mode. The filter paper diffusion method, colony counting method, and minimum inhibitory concentration (MIC) were employed to investigate the synergistic inhibitory properties and inhibitory mechanism of Ag@Kanamycin against Gram-negative Escherichia coli (E. coli), Gram-positive Staphylococcus aureus (S. aureus), and fungus Candida albicans (C. albicans). The inhibitory activity demonstrated that the MIC of the composites against the three tested bacteria was 40, 20 and 10 μg/mL, respectively. The mechanism of bacterial inhibition showed that the composites were effective in altering the permeability of the bacterial cell membrane and disrupting the cell wall, leading to bacterial apoptosis.
黄豆黄素和黄豆黄苷抗癌作用机制差异分析
施婷婷1，贾立维1，董辉1，田园1，孟鑫*1, 2
（1. 黑龙江中医药大学，药学院，黑龙江 哈尔滨 150040；2. 浙江大学，药学院，浙江 杭州 310058）
摘要：近年来，乳腺癌已超过肺癌成为最常见的癌症。此外，宫颈癌也对妇女的生活造成重大负担。细胞色素酶CYP1B1在肝外组织中的表达是这些癌症发病的关键因素，因此通过破坏CYP1B1酶与底物的结合，或消除其反应产物，是实现保护人类健康的方法。黄豆黄素和黄豆黄苷是从大豆中提取的两种异黄酮类化合物，具有抗癌的潜力，然而它们的作用机制尚不清楚。通过体外实验证明二者的抗癌作用存在差异，并通过结构和量子化学计算等研究辅助分析构效差异，分析了他们在抗癌作用中的作用机制，并发现他们的结构差异可能是作用机制差异的原因，为未来更多抗癌药物的开发提供了理论基础。
关键词：黄豆黄素；黄豆黄苷；CYP1B1；酶；癌症；抑制活性
中图分类号：R979.1+9 文献标识码：A 文章编号：0258-3283（2024）12-0048-06
DOI：10.13822/j.cnki.hxsj.2024.0242
Analysis of the Different Anti-Cancer Mechanisms between Glycitein and Glycitin SHI Ting-ting1, JIA Li-wei1, DONG Hui1, TIAN Yuan1, MENG Xin*1, 2 (1. School of Pharmacy, Heilongjiang University of Chinese Medicine NO.24 Heping Road, Harbin 150040, China; 2. School of Pharmacy, Zhejiang University, Hangzhou 310058, China)
Abstract：Breast cancer has become the most common cancer in recent years, surpassing lung cancer. Cervical cancer also poses a significant burden on women's lives. The pathogenesis of these cancers is closely related to the expression of the cytochrome enzyme CYP1B1 in extrahepatic tissues. Therefore, protecting human health could be achieved by disrupting the binding of the CYP1B1 enzyme to its substrates or by eliminating its reaction products. Glycitein and glycitin are two isoflavones extracted from soybeans that have potential anti-cancer properties. However, their mechanism of action is still unclear. In vitro experiments showed differences in their anticancer effects. Structural and quantum chemical calculations were used to analyze the differences in structure-activity relationship and mechanism of anticancer effects, which may be the mechanism of action. These findings provide a theoretical basis for designing anti-cancer drugs in the future.
【功能材料】
羟基磷灰石在蛋白吸附/分离中的研究进展
望兆博*1，江山竹1，覃阳洁1，池汝安1，黄胜超1，马会娟2，李中军1
(1. 湖北三峡实验室，湖北 宜昌 443007；2. 湖北兴发化工集团股份有限公司，湖北 宜昌 443007)
摘要：蛋白吸附/分离技术在生物制药、食品工业等领域具有重要意义，羟基磷灰石（HAP）及其衍生复合材料因其优异的吸附特性和生物相容性成为备受关注的新型蛋白吸附/分离材料。通过文献分析法，回顾了蛋白质在HAP中的吸附/解吸机理，介绍了HAP化学特性、蛋白纯化方案、色谱柱的制备，总结了近十几年HAP及其衍生复合材料在蛋白吸附方面的研究，发现HAP复合材料比表面积更大、功能性更丰富、重复使用性更好，在蛋白吸附/分离领域具有巨大的潜力和前景。旨在为该领域研究人员提供系统、准确的参考，并刺激该研究领域新材料及应用的发展。
关键词：羟基磷灰石；色谱柱；复合材料；蛋白质；吸附/分离
中图分类号：TQ174 文献标识码：A 文章编号：0258-3283（2024）12-0054-08
DOI：10.13822/j.cnki.hxsj.2024.0306
Research Progress of Hydroxyapatite in Protein Adsorption/Separation WANG Zhao-bo*1, JIANG Shan-zhu1, QIN Yang-jie1, CHI ru-an1, HUANG Sheng-chao1, MA Hui-juan2, LI Zhong-jun1 (1. Hubei Three Gorges Laboratory, Yichang 443007, China; 2. Hubei Xingfa Chemical Group Co., Ltd., Yichang 443007, China)
Abstract：Protein adsorption/separation technology is of great significance in the fields of bio-pharmaceutical and food industry. Hydroxyapatite (HAP) and its derived composite materials have become a new type of protein adsorption/separation materials because of their excellent adsorption properties and bio-compatibility. The adsorption/desorption mechanism of protein in HAP was reviewed by literature analysis. The chemical properties of HAP, the purification scheme of protein and the preparation of chromatographic column were introduced. The research on protein adsorption of HAP and its derivative composites in recent years was summarized. The results show that HAP composites have larger specific surface area, richer functionality and better reusability, which have great potential and prospect in the field of protein adsorption/separation. The aim of the review is to provide a systematic and accurate reference for researchers and stimulate the development of new materials and applications in this field.
C107e树脂对重金属离子的吸附行为研究
王佳琳，付秋平*
(贵阳学院 材料科学与工程学院，贵州 贵阳 550005)
摘要：酸性废水对人类健康和环境安全构成严峻威胁。含特定官能团的离子交换树脂可与废水中重金属离子发生交换，从而减去其负面影响。目前，酸性官能团树脂在弱酸介质中对重金属离子的选择吸附性能及吸附动力学暂不明晰，因此将含Cu2+、Fe2+、Pb2+、Zn2+的乙酸溶液模拟酸性废水，通过固定床连续流动吸附的方式，考察弱酸阳离子树脂C107e的吸附性能和穿透曲线，并用4种经验模型进行拟合。结果显示，该树脂在弱酸介质中对4种重金属离子具有明显的选择性吸附效果，亲和力排序为Pb2+>Cu2+>Fe2+>Zn2+。经过48 h的吸附，Pb2+、Cu2+、Fe2+、Zn2+的总吸附容量分别为39.83 mg/g、38.98 mg/g、32.00 mg/g、29.99 mg/g。Thomas、Yoon-Nelson和Modified dose-response模型均能很好地描述4种重金属离子的穿透曲线，但适用场景不同。
关键词：重金属；水处理；吸附；穿透曲线；模型拟合
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）12-0062-09
DOI：10.13822/j.cnki.hxsj.2024.0310
Study on the Adsorption Behavior of C107e Resin on Heavy Metal Ions WANG Jia-lin, FU Qiu-ping* (School of Materials Science and Engineering , Guiyang University, Guiyang 550005, China)
Abstract：Acidic wastewater poses a serious threat to human health and environmental safety. Ion exchange resins with specific functional groups can selectively adsorb and remove heavy metal ions in wastewater, thereby reducing their negative impacts. Currently, the selective adsorption performance and adsorption kinetics of resins with acidic functional groups for heavy metal ions in weak acid media are not clear. Therefore, the acetic acid solution containing Cu2+, Fe2+, Pb2+ and Zn2+ was simulated as acidic wastewater. The adsorption performances and breakthrough curves of weak acid cationic resin C107e were investigated by continuous flow adsorption in fixed bed, and four empirical models were used to fit. The results showed that the resin had obvious selective adsorption effect on the four heavy metal ions in weak acid media with the affinity as Pb2+>Cu2+>Fe2+>Zn2+. After 48 hours, the total adsorption capacities of Pb2+, Cu2+, Fe2+ and Zn2+ were 39.83 mg/g, 38.98 mg/g, 32.00 mg/g and 29.99 mg/g, respectively. The Thomas, Yoon-Nelson and Modified dose-response models all described the breakthrough curves of the four heavy metal ions well, but the application scenarios were different.
引用本文：王佳琳，付秋平. C107e树脂对重金属离子的吸附行为研究[J]. 化学试剂，2024，46（12）：62-70 .
聚苯胺@膨胀石墨复合材料的吸附性能研究
刘富晨，陶玉仑*，孙宇，王昊楠
（安徽理工大学 材料科学与工程学院，安徽 淮南 200235）
摘要：为了消除染料对环境的污染，使用4种酸、膨胀石墨(GIC)为掺杂剂，过硫酸铵为氧化剂，采用原位聚合法制备了聚苯胺/膨胀石墨复合材料吸附剂。利用紫外，SEM等手段对材料进行表征。结果表明，材料成功制备，具有纳米棒状结构。使用聚苯胺/膨胀石墨复合材料进行吸附实验，研究了吸附剂质量、温度、pH值等因素对吸附条件的影响。吸附实验表明对染料的去除率达到95%以上。吸附动力学曲线表明吸附过程符合准二级动力学，以化学吸附为主。
关键词：吸附；聚苯胺；复合材料；化学吸附；吸附动力学
中图分类号：TS244 文献标识码：A 文章编号：0258-3283（2024）12-0071-05
DOI：10.13822/j.cnki.hxsj.2024.0340
Adsorption properties of polyaniline @ expanded graphite composites LIU Fu-chen1, TAO Yu-lun*1, SUN Yu1, WANG Hao-nan1 (1a. School of material engineering, Anhui University of Science and Technology, Huainan 200235, China)
Abstract：In order to eliminate the environmental pollution caused by dyes, the adsorbent of polyaniline/expanded graphite composite was prepared by in-situ polymerization using four kinds of acids, expanded graphite (GIC) as dopant and ammonium persulfate as oxidant. The materials were characterized by UV and SEM. The results showed that the material was successfully prepared and had a nanorod-like structure. The adsorption experiments of polyaniline/expanded graphite composites were carried out to study the effects of adsorbent quality, temperature, pH value and other factors on the adsorption conditions. The adsorption experiment showed that the removal rate of dye was over 95%. The adsorption kinetic curves indicate that the adsorption process is consistent with quasi-secondary kinetics and is dominated by chemisorption.
【分离提取技术】
秦岭地区植物精油的提取方法及成分研究进展
王瑞婷1，何媛*2，马养民1，李小斌2，邓宝安2，马思悦1
(1. 陕西科技大学 化学与化工学院，陕西 西安 710021；2．陕西中烟工业有限责任公司，陕西 西安 710065)
摘要：秦岭是我国天然香料植物资源最丰富的地区之一。从香料植物精油的提取方法及其化学组成两方面，综述了该领域的研究现状，旨在深化对秦岭香料植物的了解与应用。通过对传统提取工艺（如水蒸气蒸馏、热回流等）与前沿技术（超临界CO2萃取、微波辅助提取、超声波辅助提取等）的系统分析，揭示了不同方法的技术优势与局限性。期望通过此项研究，为未来秦岭特色植物精油的提取与应用提供有价值的参考，进一步推动该地区自然资源的高效与可持续利用，并为天然香料植物资源的开发与利用提供新的思路和方法。
关键词：秦岭地区；植物精油；提取方法；香料提取；成分分析
中图分类号：TQ654+2 文献标识码：A 文章编号：0258-3283（2024）12-0076-11
DOI：10.13822/j.cnki.hxsj.2024.0312
Progress of Extraction Methods and Composition of Essential Oils from Plants in Qinling Region WANG Rui-ting1, HE Yuan*2, MA Yang-min1, LI Xiao-bin2, DENG Bao-an2, MA Si-yue1 (1.College of Chemical Engineering, Shaanxi University of Science & Technology；Xi'an 710021, China; 2. China Tobacco Shaanxi Industrial Co., Ltd., Xi'an 710075, China)
Abstract：The Qinling region is one of the richest regions in China in terms of natural spice plant resources. The current research status of the field is reviewed in terms of both the extraction methods and the chemical compositions of essential oils from spice plants, aiming to deepen the understanding and application of Qinling spice plants. The technical advantages and limitations of the different methods are revealed through a systematic analysis of traditional extraction processes (including hydrodistillation, and thermal reflux) and cutting-edge technologies (including supercritical CO₂ extraction, subcritical extraction). It is expected that this study will provide valuable references for the future extraction and application of essential oils of plants featured in the Qinling Mountains, which will further promote the efficient and sustainable utilization of the rich natural resources in this region, and provide new ideas and methods for the development and utilization of natural spice plant resources.
【化学品与环境】
水溶性荧光探针在可溶性污染物快速检测中的应用
吴宏梅1，徐楷1，成怀刚*1,2，丁丹婧1，李岩1，吕宏洲1
（1. 山西大学 环境与资源学院 资源与环境工程研究所，山西省黄河实验室，山西 太原 030032；
2. 青海大学 化工学院，青海 西宁 810016）
摘要：工业废水中的可溶性污染物种类繁多、污染范围广，污染物排放后迁移变化规律差异大，需要有效的方法来实时检测工业污染物。荧光探针检测技术可以对污染物进行快速有效识别和实时检测，其中水溶性荧光探针具有更高的灵敏性、水溶性、低毒性等多种优点，因而在污染物检测应用中已成为研究热点。本文综述了可用于检测可溶性污染物的荧光探针，讨论了其设计原理及传感机制。此外，还讨论了水溶性荧光探针在合成及应用过程中需要突破的局限性和挑战，并对水溶性荧光探针在化学、环境科学、生物等领域的发展前景进行了展望。
关键词：荧光探针；水溶性；快速识别；实时检测；低毒性
中图分类号：X832 文献标识码：A 文章编号：0258-3283（2024）12-0087-08
DOI：10.13822/j.cnki.hxsj.2024.0330
Application of Water-Soluble Fuorescent Probes in Rapid Detection of Soluble Pollutants Wu Hong-mei1, Xu Kai1, Cheng Huai-gang*1,2, Ding Dan-jing1, Li Yan1, Lu Hong-zhou 1 (1. Shanxi Yellow River Laboratory, Institute of Resources and Environmental Engineering, College of Environment and Resources, Shanxi University, Taiyuan 030032, China; 2. College of Chemical Engineering, Qinghai University, Xining 810016, China)
Abstract: There are many kinds of soluble pollutants in industrial wastewater, and the pollution range is wide. There are great differences in the migration and variation of pollutants after discharge. Effective methods are urgently needed to detect industrial pollutants in real time. Fluorescent probe detection technology can quickly and effectively identify and detect pollutants in real time. Among them, water-soluble fluorescent probes have many advantages such as higher sensitivity, water solubility and low toxicity, so they have become a research hotspot in the application of pollutant detection. In this paper, fluorescent probes that can be used to detect soluble pollutants are reviewed, and their design principles and sensing mechanisms are discussed. In addition, the limitations and challenges that need to be broken through in the synthesis and application of water-soluble fluorescent probes are discussed, and the development of water-soluble fluorescent probes in the fields of chemistry, environmental science and biology are prospected.
【分析与测试】
基于两种苯并稠环化合物的核磁共振氢谱研究
张飞*a，丁雅丽*b，张华山b
(青海民族大学 a. 药学院，b. 化学与材料科学学院, 青海 西宁 810007）
摘要：为了解决部分苯并稠环化合物因在溶剂中不稳定、结构类似不易区分而难以表征的问题，以1-茚酮Z-a、E-a和溶剂中不稳定的异苯并呋喃b为例，变换氘代溶剂、改变浸泡时间、加酸、加碱进行1H NMR实验研究，结果表明1-茚酮a以Acetone-d6为溶剂、异苯并呋喃b以DMSO-d6为溶剂的方法效果最佳。通过研究取代基效应对1-茚酮和异苯并呋喃特征氢化学位移的影响，结果表明获取的1H NMR实验方法可靠、取代基效应对两类化合物特征氢的化学位移影响小。苯并稠环化合物1H NMR的研究丰富了苯并稠环化合物的波谱数据，也对该类化合物结构的表征提供方法。
关键词：苯并稠环化合物；1-茚酮；异苯并呋喃；核磁共振氢谱；取代基效应；化学位移
中图分类号：O656.4 文献标识码：A 文章编号：0258-3283（2024）12-0095-08
DOI：10.13822/j.cnki.hxsj.2024.0366
Study on the Proton Nuclear Magnetic Resonance Spectra (1H NMR) Based on Two Types of Benzo-fused Polycyclic Compounds ZHANG Fei*a, DING Ya-li*b, Zhang Hua-shanb (a. College of Pharmacy, b. College of Chemistry and Materials Science, Qinghai Minzu University, Xining 810007, China)
Abstract: To address the issues with certain benzo-fused polycyclic compounds that are difficult to characterize due to instability in solvents and structural similarity, 1H NMR experimental studies were conducted using 1-indanone Z-a, E-a and the solvent-unstable isobenzofuran b as examples by using different deuterated solvents, altering the soaking time, and adding acid and base. The results showed that the optimal method for 1-indanone a was using acetone-d6 as the solvent; while for isobenzofuran b, DMSO-d6 was the best solvent. By studying the effects of substituents on the chemical shifts of characteristic hydrogens in 1-indanone and isobenzofuran, the results demonstrated that the obtained 1H NMR experimental method was reliable and that the substituent effects on the chemical shifts of characteristic hydrogens in these two types of compounds were minimal. The study of 1H NMR of benzo-fused polycyclic compounds enriched the spectroscopic data of these compounds and provided methods for the characterization of their structures.
液相色谱串联质谱法测定黄瓜中苯醚菌酯残留量
张闯1，王永芳2，刘姗姗1，潘红蕊1
（1. 天津海关工业产品安全技术中心 天津 300457;2. 天津海关动植物食品检测中心 天津 300457）
摘要：首次建立液相色谱－串联质谱（LC-MS/MS）法测定黄瓜中苯醚菌酯残留量的方法。选择QuEChERS（快速、简单、便宜、高效、耐用、安全）前处理方法进行样品提取、净化，经C18色谱柱进行色谱分离和分析，以乙腈和0.1%甲酸水为流动相进行梯度洗脱，正离子（ESI+）多反应监测模式（MRM）监测，采用基质标准曲线外标法进行定量。结果表明在10～200 μg/kg范围内线性关系良好，相关系数R2>0.99。方法的定量限为10 μg/kg，检出限为4 μg/kg。在空白黄瓜基质中添加10、40、100 μg/kg 3个浓度进行加标回收实验，回收率在76.6%～91.3%范围内, 相对标准偏差在3.7%～8.3%范围内。检测方法简便、快速、准确、灵敏度高，适用于黄瓜中苯醚菌酯残留量的测定。
关键词：苯醚菌酯；液相色谱－串联质谱；黄瓜；QuEChERS；ESI+
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2024）12-0103-06
DOI：10.13822/j.cnki.hxsj.2023.0796
Determination of Bemystrobin Residues in Cucumber by Liquid Chromatography-tandem Mass Spectrometry Zhang Chuang1，Wang Yong-fang2，Liu Shan-shan1，PAN Hong-rui1（1. Tianjin Customs Industrial Product Safety Technology Center, Tianjin 300457, China; 2. Tianjin Customs Animal and Plant Food Testing Center, Tianjin 300457, China）
Abstract: In this study, a method for the determination of bemystrobin residues in cucumber by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was established for the first time. QuEChERS (quick, simple, cheap, efficient, durable, and safe) pretreatment method was selected for sample extraction and purification. The chromatographic separation and analysis were performed on a C18 column. Acetonitrile and 0.1% formic acid water were used as the mobile phases for gradient elution. Positive ion (ESI+) multi-reaction monitoring mode (MRM) was employed, and the matrix standard curve external standard method was used for quantification. The results showed that the linear relationship was good in the range of 10～200 μg/kg with the correlation coefficient R2>0.99. The limit of quantification was 10 μg/kg, and the detection limit was 4 μg/kg. Three concentrations of 10, 40, and 100 μg/kg were added to the blank cucumber matrix for spiked recovery experiments. The recovery rates were in the range of 76.6%～91.3%, and the relative standard deviations were in the range of 3.7%～8.3%. The detection method is simple, rapid, accurate, and highly sensitive, which is suitable for the determination of bemystrobin residues in cucumber.
【合成与工艺技术】
3,3',4,4'-联苯四甲酸二酐合成的研究进展
张秀红*，张恒，王培奇，付裕轩，彭浚峰
（大连理工大学 化学学院，辽宁 大连 116024）
摘要：聚酰亚胺是迄今为止耐热温度最高的耐热树脂，综合性能位居高性能聚合物材料金字塔的顶端。以联苯四甲酸二酐合成的聚酰亚胺的性能最为优越，广泛应用于太阳能电池、航天航空、液晶领域。综述了各种以不同原料合成3,3',4,4'-联苯四甲酸二酐或者3,3',4,4'-四甲酸的方法，阐述了其制备方法的最新进展，并对3,3',4,4'-联苯四甲酸二酐合成方法的发展进行了展望。
关键词：聚酰亚胺；3,3',4,4'-联苯四甲酸二酐；3,3',4,4'-联苯四甲酸；偶联反应；有机合成；金属催化
中图分类号：TQ245.2 文献标识码：A 文章编号：0258-3283（2024）12-0109-08
DOI：10.13822/j.cnki.hxsj.2024.0381
Research Progress in the Synthesis of 3,3',4,4'-Biphenyl Tetracarboxylic Dianhydride ZHANG Xiu-hong, ZHANG Heng, WANG Pei-qi, FU Yu-xuan, PENG Jun-feng (School of Chemistry，Dalian University of Technology, Dalian 116024, China)
Abstract: Polyimide is the most heat-resistant resin to date, with comprehensive performance ranking at the top of the pyramid of high-performance polymer materials. Polyimide synthesized from biphenyl tetracarboxylic dianhydride has the most superior properties and is widely used in solar cells, aerospace, and liquid crystal fields. This article reviews various methods for synthesizing 3,3',4,4'-biphenyl tetracarboxylic dianhydride or 3,3',4,4'-biphenyl tetracarboxylic acid from different raw materials, elaborates the latest progress in their preparation methods and provides an outlook on the development of synthetic method of 3,3',4,4'-biphenyl tetracarboxylic dianhydride.
