【综述与专论】

吲哚类生物碱的抗肿瘤作用机制研究进展

权慧艳¹，陈玉琳¹，商洪玉¹，金玉雪¹，何述钟^1,2，杨岚^*1,2

（1. 贵州大学 药学院，贵州 贵阳  550025；2．贵州省合成药物工程实验室，贵州 贵阳  550025）

摘要：吲哚类生物碱是一类重要的杂环生物碱，因来源广、结构多样、药理作用广泛而成为抗肿瘤药物研究热点，其抗肿瘤机制涵盖诱导凋亡、抑制侵袭、调控细胞周期与miRNA、促进自噬及增强免疫等多个方面，在肿瘤治疗领域具有巨大的开发潜力。结合文献，针对吲哚类生物碱的抗肿瘤作用机制进行综述，以期为进一步研究和应用提供参考。

关键词：吲哚类生物碱；抗肿瘤；作用机制；研究进展；信号通路

中图分类号：O626.24            文献标识码：A         文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0400

Research Progress on the Anti-tumor Mechanism of Indole Alkaloids QUAN Hui-yan¹, CHEN Yu-lin¹, SHANG Hong-yu¹, JIN Yu-xue¹, HE Shu-zhong^1,2, YANG Lan^*1,2(1. College of Pharmacy, Guizhou University, Guiyang 550025, China; 2. Guizhou Provincial Engineering Laboratory for Synthetic Drugs, Guiyang 550025, China)

Abstract：As an important class of heterocyclic alkaloids, indole alkaloids have become a research hotspot in anti-tumor drugs, because of their wide sources, diverse structures, and broad pharmacological effects. The anti-tumor mechanisms of indole alkaloids encompass multiple aspects, such as inducing apoptosis, inhibiting invasion, regulating cell cycle and miRNA, promoting autophagy, and enhancing immunity, which shows great potential for development in the field of tumor treatment. The anti-tumor mechanisms of indole alkaloids based on existing literature were summarized. It aimed to provide reference for further research and application.

Key Words：indole alkaloid; anti-tumor; mechanism; research progress; signaling pathway

过二硫酸盐在农药和医药中间体合成中的应用

吕雷阳^*1,3，高龙强²，温光永³，陈凯⁴

(1. 中国人民大学 化学与生命资源学 光转换材料与生物光子学实验室，北京  100872；2. 福建省展化化工有限公司研发部，福建 三明  365300；3. 福建省三明市清流县高级职业中学 化工专业教研室，福建 三明  365300；4. 三明学院 资源与化工学院，福建 三明  365004)

摘要：过硫酸盐是一种廉价、易于操作和环境友好的强氧化剂，广泛应用于有机合成、电子工业、土壤修复、纺织印染、造纸、矿产开采、医用消毒等领域。在加热、光照或过渡金属存在条件下，过硫酸盐可分解生成硫酸根自由基负离子(SO₄^-•)，这种自由基负离子具有很强的单电子氧化性，能够氧化多种中性分子或负离子，生成相应的自由基活性中间体，后续可进行一系列化学转化，从而构建结构多样性的化合物。主要介绍过二硫酸盐在农药和医药中间体合成中的应用，包括氯虫苯甲酰胺类杀虫剂、抗精神病药物依匹哌唑、抗肿瘤药物替吡法尼、西地那非、单环β-内酰胺类抗生素、生物碱Botryllazine A以及萜类(+)-Chromazonarol等，期望能够进一步开发过硫酸盐在有机合成和制药领域的更多应用。

关键词：过硫酸盐; 氧化剂; 自由基; 农药中间体; 医药中间体; 有机合成

中图分类号：O626              文献标识码：A              文章编号：0258-3283(2025)--

DOI：10.13822/j.cnki.hxsj.2024.0445

Application of Persulfate in the Synthesis of Pesticides and Pharmaceutical Intermediates LV Lei-yang*^1,3, GAO Long-qiang², WEN Guang-yong³, CHEN Kai⁴ (1. Key Laboratory of Advanced Light Conversion Materials and Biophotonics, School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China; 2. Department of Research and Development, Fujian ZhanHua Chemical Co., Ltd., Sanming 365300, China; 3. Department of Chemical Engineering, Qingliu Senior Vocational High School, Sanming 365300, China; 4. School of Resources and Chemical Engineering, Sanming University, Sanming 365004, China)

Abstract：Persulfate is an economical, easy to operate, and environmentally friendly strong oxidant, which is widely used in organic synthesis, electronics industry, soil remediation, textile printing and dyeing, papermaking, mineral mining, medical disinfection, and other fields. Upon exposure to heat, light, or transition metals, persulfate can be decomposed into sulfate radical anions (SO₄•⁻). These radical anions exhibited robust single electron oxidation capabilities, which can oxidize a variety of neutral molecules or anions to form the corresponding free radical active intermediates. This facilitates a multitude of chemical transformations, allowing for the construction of structurally diverse molecules. This review primarily discussed the application of persulfate in the synthesis of pesticides and pharmaceutical intermediates, including chlorantraniliprole insecticides, antipsychotic drug epipiprazole, antitumor drug tipifarnib, sildenafil, monocyclic β-lactam antibiotics, alkaloid Botryllazine A and terpene (+)-Chromazonarol, etc. It is expected to further develop more applications of persulfate in in organic synthesis and pharmaceutical fields.

Key words: persulfate; oxidant; free radical; pesticide intermediate; pharmaceutical intermediate; organic synthesis

【生化与药用试剂】

基于DAPI介导纳米金聚集的呼吸道合胞病毒检测

许永杰¹，严艳琴¹，刘兴梅¹，安仕刚¹，黄俊²，张华^*1

(1. 贵州省人民医院 检验科，贵州 贵阳  550002；2. 贵州大学 材料与冶金学院，贵州 贵阳  550025)

摘要：纳米金比色法是一种应用前景广阔的可视化即时检测，然而盐诱导的纳米金聚集仍存在比色信号变化弱的问题，不利于肉眼判读结果，有待探究新型纳米金聚集诱导剂。4,6二脒基-2-苯基吲哚(4',6-diamidino-2-phenylindole,DAPI)是一种带正电荷的细胞核DNA染料，推测其通过电荷吸引作用介导表面带有负电荷的纳米金聚集。比色实验表明，DAPI可介导纳米金聚集，促使酒红色纳米金转变为蓝色，此信号变化优于盐诱导法。根据DAPI嵌入AT碱基双链DNA的特性，巧妙构建循环链置换聚合反应等温扩增体系；体系中富含AT碱基的扩增产物吸附DAPI至双链DNA，阻断其介导的纳米颗粒聚集，从而建立DAPI作为新型诱导剂的纳米金比色法。方法操作简单、比色变化显著，检测限为3.8 fmol/L，特异性强，有望应用于呼吸道合胞病毒的即时检测。

关键词：纳米金；等温扩增；呼吸道合胞病毒；生物传感；比色法

中图分类号：R-33      文献标识码：    文章编号：0258-3283(2025)

DOI：10.13822/j.cnki.hxsj.2024.0414

Detection of  Respiratory Syncytial Virus Based on DAPI-mediated Aggregation of Gold Nanoparticles XU Yong-jie¹, YAN Yan-qin¹, LIU Xing-mei¹, AN Shi-gang¹, HUANG Jun², ZHANG Hua^*1 (1. Department of Clinical Laboratory, Guizhou Provincial People's Hospital, Guiyang 550002, China; 2. College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China)

Abstract: The gold nanoparticles-based colorimetric sensing system is a visual real-time detection with broad application prospects. However, the salt-induced gold nanoparticle detection system still has the shortcoming of weak colorimetric signal change, which is not conducive to the visual interpretation of the results. It is highly needed to explore a new reagent to induce the aggregation of gold nanoparticles with more significant changes in colorimetric signal. 4',6-diamidino-2-phenylindole (DAPI) is a positively charged nuclear DNA dye. It is speculated that DAPI, filled with negative charges on the surface, can mediate the aggregation of gold nanoparticles through positive and negative charge attraction. Colorimetric experiments showed that DAPI can be used as a novel inducer to mediate the aggregation of gold nanoparticles, which promotes the transformation of gold nanoparticles from burgundy into blue. The change of colorimetric signal by DAPI is better than that of salt inducers. According to the intercalation characteristics of DAPI and AT-based double-stranded DNA, an isothermal amplification system of cyclic strand displacement polymerization reaction was precisely constructed. The amplification products rich in AT bases of this system adsorbed DAPI to double-stranded DNA and blocked DAPI-mediated nanoparticle aggregation, thereby establishing a gold nanoparticle colorimetric method using DAPI as a new inducer. This method is simple and has significant chromogenic signal changes. The detection limit is 3.8 fmol/L, and the specificity is strong. It is expected to be applied to the real-time detection of respiratory syncytial virus.

Key words: gold nanoparticles; isothermal amplification; respiratory syncytial virus; biosensing; colorimetry

【功能材料】

葛根素表面分子印迹聚合物吸附性能研究

及固相萃取条件优化

杨海煜，苏健，罗炳有，李俊潮，钟海艺^*

(广西中医药大学 药学院，广西 南宁 530200)

摘要：使用葛根素作为模板，配合丙烯酰胺(AM)作为功能单体，二甲基丙烯酸乙二醇酯(EDGMA)作为交联剂，以及偶氮二异丁腈(AIBN)作为引发剂，并添加适量的纳米二氧化硅作为表面载体，采用沉淀聚合法制备表面分子印迹聚合物(SMIPs)。吸附实验结果表明，该SMIPs对葛根素具有显著的吸附作用，在吸附液浓度为1.1 mg/mL时，吸附量可达11.9 mg/g。吸附过程符合Freundlich等温吸附模型，显示良好的吸附效果和应用潜力。材料对葛根素展现出特定的选择性。在固相萃取过程中，最优的上样、淋洗和洗脱条件分别为20 %、20 %和无水甲醇溶液。这项研究为从天然药物中分离、纯化和富集异黄酮类成分，特别是葛根素，提供了新颖的方法和思路。

关键词：葛根素；表面分子印迹；吸附；固相萃取；沉淀聚合法

中图分类号：O631.1      文献标识码：A            文章编号：0258-3283 (2025) --

DOI：10.13822/j.cnki.hxsj.2024.0412

Adsorption Properties of Surface Molecularly Imprinted Polymers of Puerarin and Optimization of Solid-phase Extraction Conditions YANG Hai-yu, SU Jian, LUO Bing-you, LI Jun-chao, ZHONG Hai-yi^* (College of Pharmacy, Guangxi University of Chinese Medicine, Nanning, 530200, China)

Abstract: Puerarin was used as a template, together with acrylamide (AM) as a functional monomer, ethylene glycol dimethacrylate (EDGMA) as a cross-linker, and azobisisobutyronitrile (AIBN) as an initiator. And adding an appropriate amount of silica nanoparticles as surface carriers, we successfully prepared surface molecularly imprinted polymers (SMIPs) targeting Puerarin by precipitation polymerization. The results of adsorption experiments showed that the SMIPs had a significant adsorption capacity for Puerarin, and the adsorption amount could reach 11.9 mg/g with an adsorbate concentration of 1.1 mg/mL. The adsorption process conformed to the Langmuir and Freundlich isothermal adsorption model, which showed good adsorption effect and application potential. And the material showed specific selectivity to Puerarin. The optimal up-sampling, elution and elution conditions during solid phase extraction were 20 %, 20 % and anhydrous methanol solution, respectively. This study provides novel methods and ideas for the isolation, purification and enrichment of isoflavonoid components, especially Puerarin, from natural medicines.

Key words: Puerarin; surface molecular imprinting; adsorption; solid-phase extraction; precipitation polymerization

雌二醇喹啉缀合物合成及对Zn²⁺荧光识别性能

展军颜^*，赵杰，甘春芳^*，黄燕敏

（南宁师范大学 广西天然高分子化学与物理重点实验室，广西 南宁  530001）

摘要：将荧光基团8-羟基喹啉偶联到雌二醇结构中，制备缀合喹啉的雌二醇分子探针（C）。通过核磁共振氢谱、碳谱及高分辨质谱对其结构进行了表征。荧光数据表明Zn²⁺使雌二醇分子在445 nm处的荧光增强10.3倍，而Cd²⁺仅为2.4倍。在Zn²⁺浓度为2×10^-5 ~ 1×10^-4 mol/L范围内呈良好的线性关系，雌二醇分子与Zn²⁺的配合常数为3.75×10⁴ M^-1；检测限低至2.18×10^-6 mol/L。Job 曲线和配合物质谱证实探针C与Zn²⁺配合比为1:1，核磁滴定和参照分子实验进一步证实C通过喹啉环和酯基与Zn²⁺配位。

关键词：荧光探针；雌二醇；锌离子；喹啉；荧光增强

中图分类号：O629              文献标识码：A              文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0421

Synthesis of Estradiol Quinoline Conjugate and Fluorescent Recognition to Zn²⁺ ZHAN Jun-yan^*, ZHAO Jie, GAN Chun-fang^*, HUANG Yan-min (Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, Nanning Normal University, Nanning 530001, China)

Abstract：Coupling the fluorescent group 8-hydroxyquinoline to the estradiol structure to prepare a quinoline conjugated estradiol molecular probe (C). The structure was characterized by ¹HNMR、¹³CNMR and HREI-MS.  Fluorescence data showed the probe C could enhance fluorescence in the present of Zn²⁺ and its fluorescence intensity increased by 10.3 times at 445 nm, while Cd²⁺ only increased by 2.4 times. A linear relationship between the concentration of Zn²⁺ in the range of 2×10^-5～1×10^-4 mol/L and fluorescence intensity was obtained for determining the binding constant (Ka=3.75×10⁴ M^-1) and limit of detection (LOD= 2.18×10^-6 mol/L). A 1:1 binding stoichiometry among probe C and Zn²⁺ was obtained using Job plot analysis and further confirmed by HRMS analysis of the complexes. The possible binding mode of probe C and Zn²⁺ was confirmed by ¹H NMR titrations and reference molecular recognition performance. The results showed that probe C coordinated with Zn²⁺through quinoline groups and ester groups.

Key words：fluorescent probe; estradiol; Zn²⁺ ion; quinoline; fluorescence enhancement

苯酚表面分子印迹聚合物的吸附性能研究

常自强^*，邓波，饶安举

(川北医学院 公共卫生学院，四川 南充  637000)

摘要：为高效分离、富集和回收废水中的苯酚提供一种新的吸附材料。以改性纳米二氧化硅为载体，采用表面分子印迹技术制备苯酚表面分子印迹聚合物（SiO₂-SMIP）和空白表面分子印迹聚合物（SiO₂-SNIP）；动态吸附、静态吸附、选择性吸附、再生吸附和竞争吸附实验用以探究其吸附性能。SiO₂-SMIP对苯酚具有良好的吸附能力，吸附过程属于单吸附层的化学吸附，可快速达到吸附平衡；SiO₂-SMIP比SiO₂-SNIP具有更多的亲和力结合位点和更高的最大表观结合量，且对苯酚具有特异的选择性吸附能力；SiO₂-SMIP经过多次循环使用后，对苯酚依然具有很好的吸附能力。SiO₂-SMIP吸附能力出色、性质稳定、特异选择性高，可作为吸附剂材料有效分离、富集和回收废水中的苯酚。

关键词：苯酚；分子印迹聚合物；选择性；吸附性能；废水处理

中图分类号：O647.3       文献标识码：A        文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0395

Study on Adsorption Properties of Phenol Surface Molecularly Imprinted Polymers CHANG Zi-qiang, DENG Bo, RAO An-ju (School of Public health, North Sichuan Medical College, Nanchong 637000, China)

Abstract: A new adsorption material for the efficient separation, enrichment, and recovery of phenol in wastewater was provided. Phenol surface molecularly imprinted polymers (SiO₂-SMIP) and blank surface molecularly imprinted polymers (SiO₂-SNIP) were prepared by a surface molecular imprinting technique using modified nanosilicon dioxide as the carrier. Dynamic adsorption, static adsorption, selective adsorption, regeneration adsorption, and competitive adsorption experiments were carried out to investigate the adsorption properties of SiO₂-SMIP and SiO₂-SNIP. The results showed that the SiO₂-SMIP has a good adsorption capacity for phenol. The adsorption process belongs to the chemisorption of a single adsorption layer， and the adsorption equilibrium can be reached quickly. SiO₂-SMIP has more affinity binding sites and a higher maximum apparent binding capacity  than SiO₂-SNIP, and has a specific selective adsorption capacity for phenol. After repeated use, SiO₂-SMIP still has a good adsorption capacity for phenol. SiO₂-SMIP has excellent adsorption capacity, stable properties, and high specific selectivity. It can be used as an adsorbent material to effectively separate, enrich, and recover phenol from wastewater.

Key words: phenol; molecularly imprinted polymers; selectivity; adsorption property; wastewater treatment

【分离提取技术】

银叶树树叶三萜类成分的提取工艺及其抗氧化活性研究

皮睿^1,2，张艳军^{* 1,2}，杨历^1,2，邓勤^1,2，尹艳镇^{* 1,2} 

(1. 北部湾大学 石油与化工学院，广西 钦州 535011；2. 广西绿色化工与新材料安全技术重点实验室，广西 钦州  535000)

摘要：为研究药用红树林植物银叶树树叶中三萜类成分的提取工艺及其抗氧化活性，以该植物树叶为原材料，探究超声提取功率、乙醇浓度、料液比、超声提取时间4个单因素对提取率的影响；在单因素实验的基础上，采用正交试验优化提取工艺；利用大孔树脂对提取所得三萜进行纯化，高效液相色谱法分析纯化前后样品中桦木酸与齐墩果酸的含量；最后对纯化三萜进行抗氧化测定。实验结果表明，最佳工艺条件为：超声提取功率240 W、乙醇浓度80 %、料液比1:70 (g/mL)、超声时间25 min，此条件下的银叶树三萜类成分提取率为9.17 %；大孔树脂纯化后的银叶树三萜纯度较纯化前提高了1.69倍；纯化前桦木酸含量为0.942 mg/g，纯化后含量为3.471 mg/g；纯化前齐墩果酸未检出，纯化后含量0.412 mg/g。对纯化后的银叶树三萜类成分进行DPPH自由基清除实验、羟基自由基清除实验和还原能力实验，其对DPPH自由基的IC₅₀为8.08 μg/mL，对羟基自由基IC₅₀为7.21 μg/mL，且还原能力随浓度的升高而增强，表明银叶树三萜类具有较好的抗氧化活性。该研究将为银叶树三萜作为抗氧化剂进一步开发利用提供数据基础。

关键词：银叶树；三萜；提取工艺；分离纯化；抗氧化活性

中图分类号：R284.2              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0396

Extraction process and Antioxidant Activity of Triterpenoids from the Leaves of Heritiera littoralis Dryand

PI Rui^1,2, ZHANG Yan-jun^* 1,2, YANG Li^1,2, DENG Qin^1,2, YIN Yan-zhen^* 1,2(1.College of Petroleum and Chemical Engineering, Beibu Gulf University;2. Guangxi Key Laboratory of Green Chemical Materials and Safety Technology, Qinzhou 535000)

Abstract：To optimize the extraction process and evaluate the antioxidant activity in vitro of triterpenoids from the medicinal mangrove plant Heritiera littoralis Dryand, The leaves of H. littoralis as raw material were choosed. The influences of four single factors including ultrasonic extraction power, ethanol concentration, solid-liquid ratio, and ultrasonic extraction time on the extraction rates were explored. Orthogonal experiments were employed to optimize the extraction conditions obtained from the single-factor experiments. The macroporous resin was used to purify the extracted triterpenoids. The contents of betulinic acid and oleanolic acid in the samples before and after purification were analyzed by high performance liquid chromatography. Finally, the antioxidant activity of the purified triterpenoids was determined. The optimal process conditions for ultrasound-assisted extraction of H. littoralis triterpenoids were determined as follows: ultrasonic extraction power 240 W, ethanol concentration 80%, material-liquid ratio 1:70 (g/mL), and ultrasonic extraction time 25 min. The extraction rate of triterpenoids under the optimal extraction conditions was 9.17%. The purity of triterpenoids purified by macroporous resin was 1.69 times higher than that  before purification. The contents of betulinic acid before and after purification were 0.942 and 3.471 mg/g, respectively. The oleanolic acid was not detected before purification and the content after purification was 0.412 mg/g. The DPPH radical scavenging experiment, hydroxyl radical scavenging experiment, and iron reduction ability experiment were conducted on the purified H. littoralis triterpenoids. The result showed that the IC₅₀ values of purified triterpenoids were 8.08 μg/mL for DPPH and 7.21 μg/mL for hydroxyl free radical. Moreover, the reducing capacity increased with the increase of concentration, indicating that H littoralis triterpenoids possessed good antioxidant activity. This study provides a data basis for the further development and utilization of H. littoralis triterpenoids as antioxidants.

Key words：Heritiera littoralis Dryand.; triterpenoid; extraction process; separation and purification; antioxidant activity

【电化学和新能源】

基于化学修饰玻碳电极的血清素生物医学传感

张少洋¹，刘晓军^{1, 2, 3}，朱春楠^{1, 2, 3}，刘超^{1, 2, 3}，郑冬云^{*1, 2, 3}

(1. 中南民族大学 生物医学工程学院，湖北 武汉  430074；2. 医学信息分析及肿瘤诊疗湖北省重点实验室，湖北 武汉  430074；3. 认知科学实验室国家民委重点实验室, 湖北 武汉  430074)

摘要：以玻碳电极为基底，多壁碳纳米管-聚溴酚蓝纳米复合膜为敏感功能材料，采用简单可控的滴涂成膜法和电化学聚合法，构建了一种新型血清素生物医学传感界面。借助于电化学技术、扫描电镜技术和交流阻抗技术对传感界面的构建和适用条件进行了优化，对传感机理进行了探讨，并对传感器的性能进行了评价。在最佳检测条件下，传感器用于血清素检测的线性范围为：2.0×10^-7～2.0×10^-5 mol/L，检出限为6.0×10^-8 mol/L，灵敏度为2.26 μA/(μmol·L^-1)。此外，该传感器性能良好，用于血清样品中血清素含量检测时，响应迅速，结果准确。

关键词：溴酚蓝；多壁碳纳米管；化学修饰电极；血清素；检测

中图分类号：O657.1              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0364

Biomedical Sensing of Serotonin based on Chemical Modified Glassy Carbon Electrode ZHANG Shao-yang¹, LIU Xiao-jun^{1, 2, 3}, ZHU Chun-nan^{1, 2, 3}, LIU Chao^{1, 2, 3}, ZHENG Dong-yun^{*1, 2, 3}(1. School of Biomedical Engineering, South-Central Minzu University, Wuhan 430074, China; 2.Hubei Key Laboratory of Medical Information Analysis and Tumor Diagnosis & Treatment, Wuhan 430074, China; 3.Key Laboratory of Cognitive Science of State Ethnic Affairs Commission, Wuhan 430074, China) 

Abstract：Using a glassy carbon electrode as the substrate and a multi-walled carbon nanotube-polybromophenol blue nanocomposite film as the sensitive functional material, a new type of serotonin biomedical sensing interface was constructed by simple and controllable drop-coating method and electrochemical polymerization method. The construction and application conditions of the sensing interface were optimized by means of electrochemical technology, scanning electron microscopy, and impedance technology. The sensing mechanism was investigated, and the performance of the sensor was evaluated. Under the optimal detection conditions, the linear range of the sensor for the detection of serotonin  ranged from 2.0×10^-7 to 2.0×10-⁵ mol/L, the detection limit was 6.0×10^-8 mol/L, and the sensitivity was 2.26 μA/(μmol·L^-1). In addition, the sensor has good performance, rapid response and accurate results when used to detect the content of serotonin in serum samples.

Key words: bromophenol blue; multi-walled carbon nanotubes; chemical modified electrode; serotonin; detection

【化学品与环境】

CuO催化分离膜活化过一硫酸盐去除水中亚甲基蓝的研究

王振霖^1a，张园^1a，吴丹^1a，张立宝²，尚小圆^1a，刘宇琪^1a，赵焕新^*1

(1.沈阳化工大学 a.环境与安全工程学院，b.沈阳市化工污染控制重点实验室，辽宁 沈阳  110142；2. 沈阳工大蓝金环保产业技术研究院，辽宁 沈阳  110013)

摘要：采用共沉淀法制备了CuO纳米片，将CuO纳米片通过加压和抽滤固定方式负载到纤维膜表面，制成催化分离膜。在温度25 ℃、pH 7、过一硫酸盐浓度为0.5 mmol/L、CuO纳米片负载量为79.58 g/m²、驱动压力为5×10^-3 MPa的条件下，催化分离膜在10 min内对20 mg/L亚甲基蓝(MB)溶液的去除率达到98%以上，纯水通量为457 L/(m²žh)。通过自由基捕获实验确定¹O₂是催化分离膜降解MB的主要活性氧物种。

关键词：膜分离技术；高级氧化技术；氧化铜；催化分离膜；亚甲基蓝

中图分类号：X522        文献标识码：A      文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0380

Study on the Removal of Methylene Blue from Water by activation of peroxymonosulfate using CuO Catalytic Separation Membrane   WANG Zhen-Lin^1a, ZHANG Yuan^1a, WU Dan^1a, ZHANG Li-bao², SHANG Xiao-yuan^1a, LIU Yu-qi^1a, ZHAO Huan-xin^*1 (1a.College of Environmental and Safety Engineering, 1b.Shenyang Key Laboratory of Chemical Pollution Control, Shenyang University of Chemical Technology, Shenyang 110142, China ;2.SUT-LONGKING Institute of Environmental Industrial Technology, Shenyang 110013, China)

Abstract: CuO nanosheets were successfully prepared by the co-precipitation method. CuO nanosheets were loaded on the fiber membrane by pressure and filtration to prepare the catalytic separation membrane. The removal rate of 20 mg/L methylene blue (MB)can reach 98% win 10 minutes with the pure water flux of 457 L/(m² h), under the conditions of temperature 25 ℃, pH 7, peroxymonosulfate  concentration of 0.5 mmol/L, CuO nanosheet loading of 79.58 g/m² and driving pressure of 5×10^-3 MPa. The radical quenching experiments confirmed that ¹O₂ was the main reactive oxygen species for the degradation of MB by the catalytic separation membrane.

ICP-MS测定土壤和沉积物中重金属的不同前处理方法对比研究

张义春

(福建省益准检测技术有限公司，福建 厦门  361021)

摘要：为了探究不同的土壤样品前处理方法对土壤重金属分析结果的影响，对比了敞开酸消解法和微波消解法在电感耦合等离子体质谱法测定土壤和沉积物中Cu、Pb、Zn、Cr、Co、Ni 6种重金属的应用效果。实验结果证实了微波消解法在灵敏度、准确性及精密度方面均显著优于敞开酸消解法。相比于敞开酸消解法，微波消解法对于Cu、Pb、Zn、Cr、Co和Ni的检出限更低，回收率更接近认定值，土壤标准物质GBW07404和GBW07408中Cr的回收率从敞开酸消解法的86.4 %和89.2 %提升至101.2 %和98.5 %。精密度方面，微波消解法的相对标准偏差（Relative standard deviation， RSD）普遍较低。土壤样品中Cu的RSD范围从敞开酸消解法的2.2 %~3.7 %降低到微波消解法的1.4 %~2.2 %。通过实际样品分析，进一步证实了微波消解法的优越性。

关键词：电感耦合等离子体质谱法；微波消解；敞开酸消解；重金属测定；样品前处理

中图分类号：O657.3              文献标识码：A              文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0388

Comparative Study on Different Pretreatment Methods for Determination of Heavy Metals in Soil and Sediments by ICP-MS ZHANG Yi-chun (Fujian Yizhun Testing Technology Co., Ltd., Xiamen 361021, China)

Abstract：The effects of different pretreatment methods on the analysis of heavy metals in soil samples were explored. The application effects of the open acid digestion method and the microwave digestion method in the determination of Cu, Pb, Zn, Cr, Co, and Ni in soil and sediment by inductively coupled plasma mass spectrometry were compared. The results confirmed that the microwave digestion method was significantly superior to the open acid digestion method in terms of sensitivity, accuracy, and precision. Compared with the open acid digestion method, the microwave digestion method had lower detection limits for Cu, Pb, Zn, Cr, Co, and Ni, and the recoveries were closer to the certified values. The recoveries of Cr in soil standard substance GBW07404 and GBW07408 increased from 86.4 % and 89.2 % with the open acid digestion method to 101.2 % and 98.5 % with the microwave digestion method, respectively. In terms of precision, the relative standard deviation (RSD) of the microwave digestion method were generally low. The RSD range of Cu in soil samples decreased from 2.2 %~3.7 % with the open acid digestion method to 1.4 %~2.2 % with the microwave digestion method. The analysis of actual samples further confirmed the advantages of the microwave digestion method.

Key words：inductively coupled plasma mass spectrometry; microwave digestion; open acid digestion; heavy metal determination; sample pretreatment

【分析与测试】

基于硅纳米粒子的荧光探针高灵敏检测牛奶中的青霉素

王升匀¹，李春荣^*1，孟铁宏¹，赵鸿宾¹，廖德君¹，陶晨¹，张祥令²

（1. 黔南民族医学高等专科学校 科技研发中心，贵州 都匀  558000；2. 贵州医科大学 基础医学院，贵州 贵阳  561113）

摘要：以N-氨乙基-Y-氨丙基三甲氧基硅烷和荧光素钠为原料，水热法合成了一种在450 nm处发射蓝色荧光的硅纳米粒子（DFC）。利用傅里叶变换红外光谱（FTIR）、X-射线光电子能谱（XPS）、透射电镜（TEM）、Zeta电位、紫外-可见吸收光谱等对DFC进行结构表征和光谱性能分析。通过将DFC与铬离子（Cr³⁺）作用，构建了一种可以检测青霉素（Penicillin G,PG）的荧光探针Cr³⁺@DFC。当PG存在时，Cr³⁺@DFC的荧光回升。在0.1～1.0 μg/mL检测浓度范围内，荧光回升效率与PG浓度呈良好的线性关系。线性方程为y=71.26x+0.478，R²=0.99，检出限为0.023 μg/mL。方法操作简便、灵敏度高，可用于牛奶样品中PG的检测，具有广阔的推广及应用前景。

关键词：硅纳米粒子；青霉素；荧光探针；牛奶样品；荧光检测

中图分类号：O65       文献标识码： A      文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0426

Highly Sensitive Detection of Penicillin G in Milk by Fluorescence Probe Based on Silicon Nanoparticle WANG Sheng-yun¹, LI Chun-rong^*1, MENG Tie-hong¹, ZHAO Hong-bin¹, LIAO De-jun¹, TAO Chen¹, ZHANG Xiang-ling² (1. Technology research and Development Center, Qiannan Medical College for Nationalities, Duyun 558000, China; 2. School of Basic Medicine, Guizhou Medical University, Guiyang 561113, China)

Abstract: The silicon nanoparticle（DFC）that emits blue fluorescence at 450 nm was synthesized by using the reagents of N-[3-(Trimethoxysilyl)propyl]ethylenediamine and fluorescein sodium salt. The structural characterization and spectral performance analysis of DFC were carried out by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), Zeta potential and ultraviolet-visible absorption spectrum. Based on the performance DFC can be quenched by Cr³⁺ ion, a fluorescent probe of Cr³⁺@DFC for the detection of penicillin G (PG) was prepared. The fluorescence of the Cr³⁺@DFC probe was recovered in the presence of PG. There was a good linear relationship between fluorescence recovery efficiency and PG concentration in  the range of 0.1 ～ 1.0 μg/mL. The detection limit is 0.023 μg/mL, and the linear equation was y=71.26x+0.478, R²=0.99. The method is easy to operate and has high sensitivity to detect PG in milk samples, which offers a promising application prospect.

Key words: silicon nanoparticle; penicillin G; fluorescence probe; milk sample; fluorescence detection

高效液相色谱-荧光法检测咖啡及其制品中3种赭曲霉毒素

张迎周¹，李艳美²，史华进³，李芳²，李庆¹，樊定艳¹，陈曦^*1

(1. 普研（上海）标准技术服务有限公司，上海  201318；2. 伊宁海关技术中心，新疆 伊宁  835000；3. 赛默飞世尔科技（中国）有限公司，上海  201206)

摘要：通过前处理和液相色谱条件的优化，建立高效液相色谱-荧光检测咖啡及其制品中赭曲霉毒素A、赭曲霉毒素B和赭曲霉毒素C含量的方法。样品经过V（1%碳酸氢钠水溶液）： V（乙腈）=40:60提取，赭曲霉毒素A免疫亲和柱富集净化，以2%乙酸水溶液-乙腈为流动相，采用梯度洗脱方式在C₁₈色谱柱分离，荧光检测法对3种赭曲霉毒素进行定性和定量分析。结果表明：赭曲霉毒素在0.1~10.0 μg/L浓度范围内呈现良好的线性关系（R²＞0.999），方法检出限均为0.1 μg/kg，定量限均为0.3 μg/kg，加标平均回收率为88.6%~95.0%，相对标准偏差为1.71%~3.15%。方法操作简单、灵敏度高、重现性好，适用于咖啡及其制品中赭曲霉毒素A、赭曲霉毒素B、赭曲霉毒素C含量的测定。

关键词：高效液相色谱；赭曲霉毒素A；赭曲霉毒素B；赭曲霉毒素C；咖啡

中图分类号：O65              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0365

Determination of Three Ochratoxins in Coffee and its products by High Performance Liquid Chromatography with Fluorescence Detection ZHANG Ying-zhou ¹, LI Yan-mei², SHI Hua-jin³, LI Fang², LI Qing ¹,FAN Ding-yan ¹,CHEN Xi^*1(1.GRA(shanghai) Standard Technology Service Co.,Ltd., Shanghai 201318, China; 2.Yining Customs Technology Center, Yining 835000, China; 3.Thermo Fisher Scientific(China) Co.,Ltd., Shanghai 201206, China)

Abstract： A method for determining the content of ochratoxin A, ochratoxin B, and ochratoxin C in coffee and its products was established using high performance liquid chromatography-fluorescence detection. This method involved optimizing the pre-treatment and liquid chromatography conditions. The ochratoxins were extracted using V（1% sodium bicarbonate）： V（acetonitrile）=40:60 and then enriched and purified using ochratoxin A immunoaffinity column. The separation was achieved using a C₁₈ chromatography column with a gradient elution consisting of 2% acetic acid aqueous solution-acetonitrile as the mobile phase. Three ochratoxins were analyzed using fluorescence detection. The results demonstrated a good linear relationship among three ochratoxins within 0.1 ～ 10.0 μg/L range, with R²＞0.999. The limits of detection and the limits of quantification were 0.1 and 0.3 μg/kg, respectively. The average recovery rate of spiked samples ranged from 88.6% to 95.0%, and the relative standard deviation was in the range of 1.71%~3.15%. This method is simple, highly sensitive, and exhibits good reproducibility, making it suitable for the determination of ochratoxin A, ochratoxin B, and ochratoxin C in coffee and its products.

Key words: high performance liquid chromatography; ochratoxin A; ochratoxin B; ochratoxin C; coffee

光电比浊法在线测定表面处理槽液中硫酸含量

马艳子¹，王岩¹，唐俊榕²，麦嘉琪²，聂洪港^1b，赵美萍^*1b

(1. 北京大学 a. 化学国家级实验教学示范中心；b. 化学与分子工程学院，北京  100871；2. 上海飞机制造有限公司，上海  201324)

摘要：开发了一种新型光电比浊法，用于在线快速准确测定表面处理槽液中的硫酸含量。该方法通过特定分散剂结合原位光谱测量技术，实现了对悬浊液体系吸收光谱的连续监测。利用含EDTA的醋酸-醋酸钠缓冲溶液，有效消除了Ce(III)等金属离子可能的干扰。方法线性范围为0.04 ~ 0.11 g/L，检测限为0.004 g/L。与传统的重量法相比，对实际样品时检测的相对误差< 2.5%。方法无需样品预处理，使用在线进样装置直接对样品进行取样检测，测定总时长不超过20 min，可广泛用于生产现场表面处理槽液中硫酸含量的在线快速分析。

关键词：硫酸；表面处理槽液；硫酸钡光电比浊法；光纤光谱；原位快速检测

中图分类号：O65              文献标识码：A              文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0434

A Photoelectric Turbidimetric Method for Online Determination of Sulfuric Acid in Surface Treatment Bath MA Yan-zi^1b, ZHAO Mei-ping^*1a (1a.National Demonstration Center for Experimental Chemistry Education, 1b. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 2. Shanghai Aircraft Manufacturing Co., Ltd., Shanghai 201324, China) 

Abstract：A novel photoelectric turbidimetric method for the rapid and accurate online determination of sulfuric acid content in surface treatment bath solutions was developed. The method utilized a specific dispersing agent combined with in-situ spectral measurement technology to monitor the absorption spectrum of the suspension system continuously. By using an acetate-sodium acetate buffer solution containing EDTA, the potential interference of metal ions such as Ce(III) was effectively eliminated. The method had a linear range of 0.04 to 0.11 g/L, with a detection limit as low as 0.004 g/L. Compared to the traditional gravimetric method, the relative error of this method in detecting actual samples was less than 2.5%. The method did not require sample pretreatment, and the total analysis time was no more than 20 minutes by using an online sampling device for direct sample testing.  It can be widely used for the online rapid analysis of sulfuric acid content in surface treatment bath solutions on production sites.

Key words：sulfuric acid; surface treatment bath; BaSO₄ turbidimetric method; optical fiber spectrum; in-situ rapid quantitative method

【合成与应用】

桦木醇-28-吲哚酯衍生物的设计合成及抗癌活性研究

潘思文^a，张英博^a，张萌^b，郭晓珊^c，卜明^d，王佳丰^*a

（齐齐哈尔医学院 a.病理学院，b.实验动物管理中心，c.护理学院，d.药学院，黑龙江 齐齐哈尔  161006）

摘要：为了寻找结构新颖、抗癌活性显著的先导化合物，以桦木醇为原料，设计并合成了一系列桦木醇-28-吲哚酯衍生物，并对合成产物进行了抗增殖活性测试、靶点预测和分子对接研究。结果表明，所有衍生物对3种癌细胞的抑制作用均优于桦木醇。其中，桦木醇-28-((6-氟)吲哚-3-)乙酸酯对3种癌细胞均表现出了低微摩尔级别的抗增殖活性（IC₅₀ < 10.00 µmol/L），其对A549细胞的作用最强（IC₅₀ = 7.25 µmol/L），是桦木醇的4.15倍。作用机制研究表明，上述化合物可能通过抑制PI3K-Akt通路发挥抗癌作用。总之，该化合物是一种具有良好抗癌活性的先导化合物，对其进一步的结构修饰和药理研究具有重要的意义。

关键词：桦木醇；吲哚；结构修饰；抗癌活性；PI3K-Akt通路

中图分类号：R914         文献标识码： A                   文章编号:0258-3283（2025）--

DOI: 10.13822/j.cnki.hxsj.2024.0382

Design, synthesis, and anticancer activity of Betulin-28-indole ester derivatives Pan Si-wen^a，ZHANG Ying-bo^a，ZHANG Meng^b，GUO Xiao-shan^c，BU Ming^d，WANG Jia-feng^*a (a. College of Pathology, b. Animal Laboratory Center, c. College of Nursing, d. College of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China.)

Abstract: In order to find lead compounds with novel structure and remarkable anticancer activity, a series of Betulin-28-indole ester derivatives were designed and synthesized from Betulin. The synthesized products were tested for anticancer activities, and target prediction and molecular docking studies were carried out in this project. The results showed that the inhibitory effects of all derivatives on the three cancer cells were better than that of Betulin. Among them, Betulin-28- ((6-fluoro) indole-3-) acetate displayed low micromolar anti-proliferative activity against three cancer cells (IC₅₀ < 10.00 µmol/L), and its effect was the strongest against A549 cells (IC₅₀ = 7.25 µmol/L), which was 4.15 times that of Betulin. The mechanism study has shown that the above compound may play an anticancer role by inhibiting the PI3K-Akt pathway. In conclusion, this compound is a promising lead compound with excellent anticancer activity, and further structural modification and pharmacological studies on it hold great significance.

Key word: Betulin; indole; structural modification; anticancer activity; PI3K-Akt pathway