【特约专题】

电化学免疫传感器在肿瘤早诊中的研究进展

赵静^1,2，邝俊玮¹，郭子政¹，尹磊¹，王振宇*^1,2

(1.大连理工大学 化工海洋与生命学院,辽宁 盘锦  124221；2.艾美诫信生物制药有限公司,辽宁 大连  116600)

摘要：肿瘤早期诊断是提高患者生存率和改善预后的关键,但传统方法存在检出滞后、操作复杂等局限。电化学免疫传感器结合免疫反应的特异性与电化学检测的高灵敏性,为肿瘤标志物的痕量检测(常低至皮摩尔-飞摩尔级)提供了新策略。系统梳理其在肿瘤早期诊断中的技术原理、信号放大策略及临床应用,旨在推动临床转化。分析生物识别元件(如抗体、适配体)与信号转导机制(无标记型如电化学阻抗谱、标记型如酶标记和纳米材料标记),信号放大策略(酶催化级联、纳米材料介导、磁珠富集等)及纳米材料创新应用(碳基材料如石墨烯/碳纳米管、金属基材料如钯纳米粒子/铁氧化物、二维材料如MXene/二硫化钼)。结果显示,该类传感器具有快速响应、低成本、易于微型化等优势,在多癌种诊断中进展显著,部分对肝癌、乳腺癌、结直肠癌等标志物的检测限已达飞摩尔级,显著提升早期诊断的灵敏度与特异性。但其仍面临生物污染、稳定性不足及临床验证匮乏等挑战,需深入研究以促进实际应用。

关键词：电化学免疫传感器；肿瘤早期诊断；肿瘤标志物；纳米材料；信号放大

中图分类号：O657           文献标识码：A             文章编号：0258-3283(2026)01-0001-11

DOI：10.13822/j.cnki.hxsj.2025.0239

Research Progress of Electrochemical Immunosensors in Early Diagnosis of Tumors  ZHAO Jing^{1, 2}, KUANG Jun-wei¹,GUO Zi-zheng¹, YIN Lei¹, WANG Zhen-yu^{*1, 2} (1. School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin 124221, China；2. AIM Honesty Biopharmaceutical Co., Ltd.‌, Dalian 116600, China) 

Abstract: Early diagnosis of tumors is crucial for improving patient survival rates and prognosis,but traditional methods suffer from limitations such as delayed detection and complex procedures.Electrochemical immunosensors,which integrate the specificity of immune reactions with the high sensitivity of electrochemical detection,provide a promising strategy for trace detection of tumor markers (often as low as picomolar to femtomolar levels).This review systematically summarized the underlying principles,signal amplification strategies,and clinical applications of electrochemical immunosensors in early tumor diagnosis,aiming to promote clinical translation.In this review,biorecognition elements (e.g.,antibodies and aptamers) and signal transduction mechanisms (label-free methods such as electrochemical impedance spectroscopy,and labeled methods such as enzyme or nanomaterial labeling) were discussed in detail.Signal amplification strategies (e.g.,enzymatic catalytic cascades,nanomaterial-mediated methods,magnetic bead enrichment) were reviewed alongside innovative applications of nanomaterials,including carbon-based materials (e.g.,graphene,carbon nanotubes),metal-based materials (e.g.,palladium nanoparticles,iron oxides),and two-dimensional materials (e.g.,MXene/molybdenum disulfide).Results showed that such sensors have advantages including rapid response,low cost,and easy miniaturization,and have made significant progress in the diagnosis of multiple cancer types.For example,detection limits for biomarkers of liver,breast,and colorectal cancer have reached the femtomolar level,significantly improving the sensitivity and specificity of early diagnosis.However,challenges such as biofouling,limited stability,and insufficient clinical validation remain.Continued research is required to enhance their robustness and accelerate clinical implementation.

Key words：electrochemical immunosensor; early tumor diagnosis; tumor marker; nanomaterial; signal amplification

植物对新污染物的吸收与代谢研究进展

周豪，周庆华^*

（浙江工业大学环境学院，浙江杭州  310014）

摘要：新污染物在环境多介质中的广泛检出已成为全球关注的焦点。植物作为生态系统的初级生产者,能够从环境介质中吸收这些污染物,并通过食物链传递对生态系统和人类健康构成风险。现有报道主要关注新污染物的植物吸收或植物代谢单一过程,且对相关影响因素的系统阐述较为缺乏。基于此,系统综述了植物对新污染物的吸收与代谢过程及其影响因素,旨在深入解析新污染物在植物中的归趋行为。植物主要通过根吸收(被动扩散/主动转运)和叶吸收(气孔/角质层渗透)途径吸收新污染物。植物吸收过程受植物特性(种类、根系分泌物、通道蛋白表达等)、污染物理化性质(极性、疏水性、分子大小等)及环境因素(土壤有机质、pH、温度等)影响。新污染物进入植物体后,在代谢酶介导下发生代谢转化反应,包括:Ⅰ相代谢(氧化、还原、水解、裂解等)、Ⅱ相代谢(与葡萄糖苷、谷胱甘肽、氨基酸等缀合)和Ⅲ相代谢(液泡或细胞壁隔离固定),最终生成水溶性更高、毒性更低的物质。植物代谢过程受植物特性(代谢酶、内源性物质等)和污染物化学结构(官能团类型、分子大小、空间构型等)影响。

关键词：新污染物；植物吸收；植物代谢；理化性质；环境因素

中图分类号：Q945.78、O6-1      文献标识码：A            文章编号：0258-3283(2026)01-0012-09

DOI：10.13822/j.cnki.hxsj.2025.0217

Advances in the Uptake and Metabolism of Emerging Contaminants in Plants  ZHOU Hao，ZHOU Qing-hua^*（College of Environment, Zhejiang University of Technology, Hangzhou 310014, China）

Abstract: The widespread occurrence of emerging contaminants (ECs) in multiple environmental media has become a global environmental concern.As primary producers in ecosystem,plants can absorb ECs from the surrounding environments and transfer them through the food chain,thereby posing potential risks to both ecosystems and human health.Previous studies have predominantly focused on either the uptake or the metabolism of ECs in plants,with limited systematic discussion of the influencing factors.Hence,this study comprehensively reviewed the uptake and metabolic processes of ECs in plants,as well as key factors affecting these processes,to provide a good understanding of the fate of ECs in plants.ECs are primarily taken up by roots (via passive diffusion or active transport) and leaves (via stomatal penetration or cuticular absorption).Plant uptake is influenced by plant traits (e.g.,species,root exudates,and channel protein expression),physicochemical properties of ECs (e.g.,polarity,hydrophobicity,and molecular size),and environmental factors (e.g.,soil organic matter,pH,and temperature).Once entering plants,ECs undergo enzyme-mediated metabolic transformations,including Phase Ⅰ metabolism (e.g.,oxidation,reduction,hydrolysis,and cleavage),Phase Ⅱ metabolism (conjugation with glucose,glutathione,amino acids),and Phase Ⅲ metabolism (compartmentalization in vacuoles or integration into cell walls).These processes convert ECs into more water-soluble and less toxic compounds.The metabolism process is affected by plant characteristics (e.g.,metabolic enzymes and endogenous substances) and the chemical structure of ECs (e.g.,functional groups,molecular size,and spatial configuration).

Key words: emerging contaminants; plant uptake; plant metabolism; physicochemical properties; environmental factors

用于识别抗肿瘤新药A166的化学功能材料的开发

孙梦婷，王冬^*，董林毅^*

（天津医科大学肿瘤医院国家恶性肿瘤临床医学研究中心天津市恶性肿瘤临床医学研究中心天津市肿瘤防治重点实验室，天津  300060）

摘要：A166 是一种靶向 HER2 的 ADC药物，主要针对HER2阳性乳腺癌及其他HER2表达的实体瘤。用药后的临床药物检测对于临床指导用药来说至关重要，不仅可以优化给药方案，以提高疗效、减少毒副作用，还可以减少耐药情况的产生。目前临床血药浓度监测（TDM）的主要方法包括免疫分析法、色谱法（如高效液相色谱法HPLC）以及新兴的床旁检测技术（如质谱法）。但是存在对操作人员要求高、价格昂贵、设备维护、步骤繁琐等缺点。为了解决A166血液浓度监测的问题，创新性地提出了将硼酸与修饰罗丹明6G荧光素负载氧化石墨烯（HR6GGO）与硼酸亲和导向表面印迹磁性纳米颗粒（MIP-A166）相结合，用于药物A166在体内的血药浓度监测。经硼酸修饰并负载大量罗丹明6G荧光素的HR6GGO材料，可通过硼酸亲和作用选择性标记A166，实现荧光信号放大与输出。成功制备了HRBGO和MIP-A166，通过实验优化，得到的MIP-A166-HRBGO策略对A166的检测具有超高灵敏度和优越的特异性。MIP-A166则借助硼酸亲和分子印迹识别机制，对模板药物表现出特异性选择能力。MIP-A166偶联HR6GG0的夹心检测策略依托双重硼酸亲和协同作用，展现出普适性应用潜力，为临床药物监测以及指导用药提供帮助。

关键词：分子印迹聚合物；血药浓度监测；A166；单抗药物；双硼酸亲和协同作用

中图分类号：O65                  文献标识码：A            文章编号：0258-3283(2026)01-0021-07

DOI：10.13822/j.cnki.hxsj.2025.0199

Development of Chemical Functional Materials for Identifying New Antitumor Drug A166  SUN Meng-ting, WANG Dong^*, DONG Lin-yi^* (Tianjin Key Laboratory of Cancer Prevention and Therapy, Tianjin’s Clinical Research Center for Cancer, National Clinical Research Center for Cancer, Tianjin Medical University Cancer Institute & Hospital, Tianjin 300060, China)

Abstract: A166 is an ADC drug targeting HER2,mainly used for the treatment of HER2-positive breast cancer and other solid tumors expressing HER2.Clinical drug monitoring after administration is crucial for clinical medication guidance,as it can optimize the dosing regiments to enhance efficacy,minimize side effects,and reduce the development of drug resistance.Currently,the main methods for therapeutic drug monitoring (TDM) include immunoassay methods,chromatography methods (such as high-performance liquid chromatography HPLC),and emerging point-of-care technologies (such as mass spectrometry).However,these methods have several drawbacks,including the need for highly trained operators,high cost,equipment maintenance,and complex procedures.To address the challenge of monitoring A166 blood concentration,a novel strategy was proposed by combining boronic acid-modified rhodamine 6G-functionalized graphene oxide (HR6GGO) with a boronic acid-affinity molecularly imprinted magnetic nanoparticle (MIP-A166).The HR6GGO material,modified with borate and loaded with a large amount of rhodamine 6G fluorescent dye,can selectively label A166 through boronic acid affinity,achieving fluorescence signal amplification and output.HRBGO and MIP-A166 were successfully prepared and the MIP-A166-HRBGO strategy achieved extremely high sensitivity and excellent specificity for the detection of A166 after experimental optimization.MIP-A166 utilizes the boronic acid affinity molecular imprinting recognition mechanism,showing specific selectivity for the template drug.The sandwich detection strategy,based on the coupling of MIP-A166 with HR6GGO,relies the dual boronic acid affinity synergism,demonstrating board application potential and providing a promising tool for clinical drug monitoring and medication guidance.

Key words: molecularly imprinted polymer; serum concentration monitoring; A166; monoclonal antibody drugs; diboronic acid affinity cooperative effect

【功能材料】

构建高催化活性的BiVO₄@Ag复合材料

蔡旭鹏，王月荣，蔡依辰，洪先健，郭少波，郭小华，季晓晖^*

(陕西理工大学 化学与环境科学学院，陕西 汉中  723000)

摘要：针对钒酸铋(BiVO₄)光催化剂存在的载流子复合率高、表面反应动力学迟缓等问题,以球形BiVO₄为基底,通过3种不同光化学还原方法(直接还原法、银氨配合物-还原法、溴化钾调控还原法)构建BiVO₄@Ag-6%复合材料,系统探究不同负载方式对材料微观结构及光催化性能的影响。利用透射电子显微镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)以及电化学测试等对复合材料的结构和性质进行了系统表征。实验结果表明,通过溴化钾调控还原法制备的目标材料具有较好催化活性。这是由于利用AgBr配合物缓释Ag⁺机制,显著优化了Ag纳米颗粒(Ag NPs)的分散度及界面结合强度,其光催化降解Cr⁶⁺和罗丹明B(RhB)的活性最佳(Cr⁶⁺在20 min内完全降解,RhB降解效率较纯BiVO₄提升明显)。结合表征分析,其优异性能归因于Ag NPs的等离子体共振效应(SPR)和肖特基势垒的协同作用,能够有效抑制载流子复合,并加速界面电荷传输。

关键词：BiVO₄；银纳米颗粒（Ag NPs）；光催化降解；等离子体共振效应（SPR）；降解率

中图分类号：O611.4          文献标识码：A         文章编号：0258-3283(2026)01-0028-08

DOI：10.13822/j.cnki.hxsj.2025.0253

Synthesis of Highly Active BiVO₄@Ag Composites with Enhanced Catalytic Performance  CAI Xu-peng, WANG Yue-rong, CAI Yi-chen, HONG Xian-jian, GUO Shao-bo, GUO Xiao-hua, JI Xiao-hui^*( School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China)

Abstract：This study addressed the issues of high carrier recombination rates and sluggish surface reaction kinetics in bismuth vanadate (BiVO₄) photocatalysts.Using spherical BiVO₄ as the substrate,BiVO₄@Ag-6% composite materials were constructed via three distinct photochemical reduction methods (direct reduction,silver-ammonia complex reduction,and potassium bromide-mediated reduction).The effects of different loading methods on the microstructure and photocatalytic performance of the materials were systematically investigated.The structure and properties of the composite materials were systematically characterized using transmission electron microscopy (TEM),X-ray photoelectron spectroscopy (XPS),X-ray diffraction (XRD),ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS),and electrochemical measurements.Experimental results indicated that the target material prepared via the potassium bromide-controlled reduction method exhibits superior catalytic activity.The AgBr complex-mediated Ag⁺ release mechanism significantly optimizes the dispersion and interfacial bonding strength of Ag nanoparticles (Ag NPs),resulting in optimal photocatalytic degradation activity for Cr⁶⁺ and Rhodamine B (RhB) with complete Cr⁶⁺ degradation within 20 min and a markedly enhanced RhB degradation efficiency compared to pure BiVO₄.Characterization analysis attributes this superior performance to the synergistic effects of surface plasmon resonance (SPR) and the Schottky barrier in Ag NPs,which effectively suppressed carrier recombination and accelerate interfacial charge transport.

Key words：BiVO₄; silver nanoparticles (Ag NPs); photocatalytic degradation; surface plasmon resonance (SPR)；degradation rate

基于便携式荧光试纸条的水体抗生素比率荧光检测方法研究

李凤兰^*a，黄碧妃^a，林泽彪^a，黄文杰^b

(福建警察学院 a.刑事科学技术系，b.侦查系，福州 福建  350007)

摘要：通过开发一种高灵敏、高选择性的新方法,以应对水环境中抗生素污染对生态环境和人类健康造成的危害。采用一步法合成沸石咪唑酯-8(ZIF-8)材料,通过FT-IR、XRD、SEM、TEM、XPS等多种表征技术对其结构进行系统分析,构建基于比率荧光的左氧氟沙星(LFX)检测传感器。在ZIF-8浓度为25 μg/mL、pH为7.0、反应时间为5 min的最佳反应条件下,所制备传感器对LFX的线性检测范围为1～80 μmol/L,检出限达0.29 μmol/L;实际水样检测回收率98.27%～101.90%,RSD≤2.99%,与HPLC结果吻合良好;开发的智能手机便携式试纸传感器可实现10～100 μmol/L范围内的实时检测。该研究为ZIF-8基荧光传感器的设计提供了新思路,建立了环境水体中痕量抗生素污染物的快速检测新方法。

关键词：ZIF-8；比率型；荧光传感器；左氧氟沙星；荧光试纸

中图分类号：O65             文献标识码：A             文章编号：0258-3283(2026)01-0036-07

DOI：10.13822/j.cnki.hxsj.2025.0214

Research on a Ratiometric Fluorescence Detection Method for Antibiotics in Water Based on Portable Fluorescent Test Strips  Li Feng-lan^*a, Huang Bi-fei^a, Lin Ze-biao^a, Huang Wen-jie^b (a.Department of Criminal Science and Technology, b.Department of Criminal Investigation, Fujian Police College, Fuzhou, Fujian 350007, China) 

Abstract： This study aims to develop a novel,highly sensitive and selective method to address the ecological and human health risks posed by antibiotic pollution in aquatic environments.Zeolitic imidazolate framework-8 (ZIF-8) was synthesized via a one-step method and systematically characterized using FT-IR,XRD,SEM,TEM,and XPS.A ratiometric fluorescence sensor was then constructed for the detection of levofloxacin (LFX).Under optimal conditions (ZIF-8 concentration:25 μg/mL,pH 7.0,reaction time:5 min),the sensor exhibited a linear detection range of 1～80 μmol/L for LFX,with a detection limit of 0.29 μmol/L.The recovery rate in real water samples was from 98.27% to 101.9%,with RSD≤2.99%,showing good agreement with HPLC results.Additionally,a smartphone-based portable test strip sensor was developed,enabling real-time detection in the range of 10～100 μmol/L.This study provides a new approach for designing ZIF-8-based fluorescence sensors and establishes a rapid detection method for trace antibiotic pollutants in environmental water.

Key words：ZIF-8; Ratiometric; Fluorescence sensor; Levofloxacin (LFX); Fluorescent test strip

【化学品与环境】

尿素-Na₂CO₃协同改性生物炭的表面自由基调控机制及PMS活化效能

马紫朝^*，董刚，刘伯渠，卢新生

（甘肃民族师范学院化学与生命科学学院，甘肃合作  747000）

摘要：为解决水体中难降解有机污染物的处理问题,治理环境污染,以苯胺为模型污染物,采用尿素与碳酸钠共掺杂协同改性玉米芯生物炭,探究其表面自由基调控机制及过氧单硫酸盐活化效能。实验通过不同氮源、尿素掺量、碳酸钠掺量及热解温度等条件的调控,制备改性生物炭,并对其自由基生成、苯胺去除效果、官能团及元素含量等进行分析。30%尿素的掺入对应的持久性自由基浓度为5.339×10⁹ spins/g,显著高于其他氮源。尿素掺量30%、碳酸钠掺量40%时,持久性自由基浓度最高,苯胺去除效果最佳;持久性自由基浓度与苯胺去除效果为正相关。同时,热解温度从300 ℃上升至 900 ℃,生物炭C的含量从6.983%上升至53.256%,H含量上升后下降至1.169%,O含量下降至20.065%,N含量上升后下降,峰值为7.142%,金属元素富集,其中Fe含量富集至9 258.477 mg/kg;此外改性生物炭的官能团逐渐减少,含氧官能团下降。持久性自由基、改性生物炭添加量是影响苯胺去除效果的关键因素,适当条件下最佳去除率可达97.6%。此外,500 ℃热解温度下制备的改性生物炭具有适中的孔隙结构和稳定的表面官能团,重复使用性能良好。尿素-碳酸钠协同改性生物炭可有效调控表面自由基,显著提升持久性自由基的活化效能,为难降解有机污染物的高效处理提供了新思路。

关键词：有机污染物；生物炭；过氧单硫酸盐；自由基；环境治理

中图分类号：O69             文献标识码：A             文章编号：0258-3283(2026)01-0043-09

DOI：10.13822/j.cnki.hxsj.2025.0229

Surface Radical Regulation Mechanism and PMS Activation Efficiency of Urea-Na₂CO₃ Synergistically Modified Biochar  MA Zi-chao^*, DONG Gang, Liu Bo-qu, LU Xin-sheng(College of Chemistry and Life Sciences, Gansu Minzu Normal University, Cooperation, Hezuo 747000)

Abstract： To address the issue of treating refractory organic pollutants in water and to control environmental pollution,this study used aniline as a model pollutant and investigated the co-doping and synergistic modification of corn cob biochar with urea and sodium carbonate.The surface free radical regulation mechanism and the activation efficiency of peroxymonosulfate were explored.Modified biochar was prepared by varying nitrogen sources,urea dosage,sodium carbonate dosage and pyrolysis temperature,and analyzed for free radical generation,aniline removal efficiency,functional groups,and elemental composition.Incorporation of 30% urea resulted in a persistent free radical concentration of 5.339×10⁹ spins/g,significantly higher than other nitrogen sources.When urea and sodium carbonate contents were 30% and 40%,respectively,the persistent free radical concentration and aniline removal efficiency were maximized,showing a positive correlation.As pyrolysis temperature increased from 300 to 900 ℃,the carbon content of biochar increased from 6.983% to 53.256%,hydrogen content initially increased and then decreased to 1.169%,oxygen content decreased to 20.065%,and nitrogen content peaked at 7.142%.Metal elements were enriched,with Fe concentration reaching 9 258.477 mg/kg.Functional groups in the modified biochar gradually decreased,especially oxygen-containing functional groups.Persistent free radicals and biochar the dosage were key factors affecting aniline removal,achieving an optimal removal rate of 97.6% under optimal conditions.Moreover,biochar prepared at 500 ℃ exhibited a moderate pore structure,stable surface functional groups,and good reusability.Urea-sodium carbonate synergistic modification effectively regulates surface free radicals,significantly enhance their activation efficiency,providing a new idea for the efficient treatment of refractory organic pollutants.

Key words：Organic pollutants; Biochar; Peroxymonosulfate; Free radicals; Environmental remediation

固定化漆酶纤维素纳米晶复合水凝胶的制备及其除污性能的研究

舒士倡^*,闫宏涛

(宁夏大学新华学院 工程与应用科学系，宁夏 银川  750021)

摘要：水污染已经成为当今环境治理中的难题,不仅造成了巨大的经济损失,更是危害到了人类的生产生活。其中难降解的酚类具有化学需氧量高、毒性大、稳定性强等特点,而且对微生物具有抑制作用,使得废水处理过程具有挑战性。采用传统均相反应所用催化剂存在催化活性低、易产生污泥、不可重复使用等缺点。水凝胶具有独特三维网状结构,对废水中污染物具有高去除率、高循环率,广泛应用在废水处理。而生物酶催化处理法具有催化效能高、反应条件温和、对废水质量及设备情况要求较低、可以重复使用等优点,使其在污水处理具有显著优势。因此,通过聚合反应将漆酶引入水凝胶三维网络结构,通过纤维素纳米晶调控水凝胶的渗透性能及力学性能,从而制备一种非均相水凝胶催化剂。研究各组分对水凝胶性能的影响,并分析漆酶纤维素纳米晶水凝胶对4种典型有机酚类有机化合物的降解效率,并总结相关技术参数,为指导水凝胶基非均相催化剂提供技术指导。

关键词：纤维素纳米晶；水凝胶；固定化酶；有机酚降解；除污性能

中图分类号：O69              文献标识码：A             文章编号：0258-3283(2026)01-0052-06

DOI：10.13822/j.cnki.hxsj.2025.0275

Preparation of Immobilized Laccase Cellulose Nanocrystal Composite Hydrogels and Their Decontamination Properties  SHU Shi-chang, YAN Hong-tao (Department of Engineering and Applied Sciences, Xinhua College of Ningxia University, Yinchuan 750021, China) 

Abstract：Water pollution has become a major challenge in contemporary environmental management,causing not only significant economic losses but also posing threats to human production and daily life.Among various pollutants,recalcitrant phenolic compounds are particular problematic due to their high chemical oxygen demand,high toxicity,and chemical stability.Furthermore,their inhibitory effects on microbial activity future increase the difficulty of wastewater treatment.Traditional homogeneous catalysts suffer from drawbacks such as low catalytic activity,sludge generation,and non-reusability.Hydrogels,featuring unique three-dimensional network structures,demonstrate high pollutant removal efficiency and excellent recyclability,and thus have been widely used in wastewater treatment.Enzymatic catalytic treatment methods,characterized by high catalytic efficiency,mild reaction conditions,low requirements for wastewater quality and equipment,and reusability,also provide significant advantages in wastewater treatment.In this work,laccase was incorporated into a three-dimensional network structure of hydrogels via polymerization reactions.By introducing cellulose nanocrystals to modulate the permeability and mechanical properties of the hydrogels,a heterogeneous hydrogel catalyst is prepared.The study investigated the effects of various components on hydrogel properties and analyzed the degradation efficiency of laccase-cellulose nanocrystal hydrogel toward four typical organic phenolic compounds.It summarized relevant technical parameters to provide guidance for hydrogel-based heterogeneous catalysts.

Key words：cellulose nanocrystals; hydrogels; immobilized enzymes; degradation of organic phenols; pollution removal performance

【分析与测试】

聚乙烯醇-碘法在线测定表面处理槽液中硼酸含量

马艳子¹，何?¹，唐俊榕²，王亚齐²，王岩¹，赵美萍*¹

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

摘要：为实现金属表面处理槽液中常量硼酸的在线快速检测，开发了一种基于反应动力学与原位光谱分析的新型测定方法。该方法系统研究了硼酸存在下聚乙烯醇（PVA）与碘三负离子（I₃^-）之间的显色反应动力学过程。通过调控反应物浓度、介质组成与温度等条件，并监测溶液吸收光谱随时间的变化，发现体系中固有的硫酸与钠离子对PVA-I₃^-显色反应具有显著促进作用，且低温条件更有利于反应进行。基于上述发现，将反应温度精确控制于20 °C，并优化介质中硫酸浓度与静电环境，在抑制槽液背景干扰的同时，显著加快了依赖于硼酸浓度的PVA-I₃^-显色反应速率。该方法在反应开始后120 s即可获得可用于定量分析的响应信号，在0 ~ 9 mmol/L硼酸浓度范围内线性关系良好，检出限为0.34 mmol/L。实际样品检测的相对误差＜1%，表明该方法具有良好的准确性与实用价值。进一步集成高精度注射泵、多通道阀与自动流路系统，构建了全自动在线检测装置。该装置可在45 min内完成校准与样品检测全过程，无需前处理步骤，适用于工业现场对槽液硼酸含量的实时监测与闭环控制。

关键词：硼酸；表面处理槽液；聚乙烯醇-碘；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(2026)01-0058-08

DOI：10.13822/j.cnki.hxsj.2025.0262

Polyvinyl Alcohol-Iodine Method for Online Determination of Boric Acid in Surface Treatment Bath  MA Yan-zi^1b, He Peng^1b, TANG Jun-rong², WANG Ya-qi², WANG Yan^1b, ZHAO Mei-ping^*1a (National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 2. Shanghai Aircraft Manufacturing Co., Ltd., Shanghai 201324, China)

Abstract：A novel method based on reaction kinetics and in-situ spectroscopic analysis was developed for the online rapid detection of boric acid in metal surface treatment bath solutions. This method systematically investigated the kinetic behavior of the chromogenic reaction between polyvinyl alcohol (PVA) and triiodide ions (I₃^-) in the presence of boric acid. By adjusting parameters such as reactant concentration, medium composition, and temperature, and monitoring the temporal changes in the solution absorption spectrum, it was found that the inherent sulfuric acid and sodium ions in the system significantly promote the PVA-I₃^- chromogenic reaction, with lower temperatures being more favorable for the reaction to proceed. Based on these findings, the reaction temperature was precisely controlled at 20 °C, and the sulfuric acid concentration and electrostatic environment in the reaction medium were optimized. This approach significantly accelerated the boric acid concentration-dependent PVA-I₃^- chromogenic reaction while effectively suppressing interference from background components in the bath solution. A reliable analytical signal suitable for quantification was obtained within 120 s after reaction initiation. The method demonstrated a good linear relationship within the boric acid concentration range of 0-9 mmol/L, with a detection limit of 0.34 mmol/L. The relative error of actual sample testing was less than 1%, indicating good accuracy and practical utility. Furthermore, a fully automated online detection system was built by integrating high-precision syringe pumps, multi-port valves, and an automated flow path system. This setup completed the entire calibration and sample detection process within 45 minutes without any pre-treatment steps, making it applicable for real-time monitoring and closed-loop control of boric acid concentration in industrial settings.

Key words：boric acid; surface treatment bath; polyvinyl alcohol-iodine; optical fiber spectrum; in-situ rapid quantitative detection

16种嗅味物质在环境水中的稳定性及样品保存试验研究

郭爱华^*，王玮，王晨，李?遥?温雅

（北京市西城区疾病预防控制中心，北京  100120）

摘要：了解环境水中16种嗅味物质的稳定性和样品最佳保存条件,以提高检测结果准确性。考察16种嗅味化合物在两种不同基质(地表水和自来水)环境水中的稳定时间,以及常见采样容器(棕色硬质玻璃容器、棕色聚乙烯容器)、保存温度(20～25 ℃常温、0～4 ℃冷藏)和常用保存剂(抗坏血酸、盐酸溶液、硫代硫酸钠)对水样中目标物稳定性的影响,采用固相微萃取-气相色谱-串联质谱法对水样中嗅味化合物进行检测。各嗅味物质随时间的延长浓度降低,萜类(2-MIB、GSM)、吡嗪类(IPMP、IBMP)在环境水中的稳定性优于酮类(β-ionone)、醛类(β-cyclocitral、2,4-HD、2,6-ND)和芳香杂环类(indole);水样采集后应置于磨口硬质棕色玻璃瓶0～4 ℃保存,聚乙烯塑料瓶存在MTBE和2,6-dichlorphenol污染溶出风险,相较于常温保存,0～4 ℃保存可缓解待测物损失速度;地表水中2,4-HD、2,6-ND、β-ionone、indole稳定性较差,自来水中2,4-HD、2,6-ND稳定性较差,其他化合物在无添加保存剂时,可保存24 h;地表水中2,4-HD、2,6-ND、β-ionone应添加盐酸保存,indole应添加抗坏血酸保存并当天测定,自来水中2,4-HD添加抗坏血酸后可保存24 h。水样中嗅味物质的稳定性不同,应根据其在不同基质水样中稳定性的差异,采用相应保存方法,确保检测结果的准确。

关键词：环境水；嗅味化合物；稳定性；样品保存；固相微萃取-气相色谱-串联质谱法

中图分类号：O69           文献标识码：A            文章编号：0258-3283(2026)01-0066-10

DOI：10.13822/j.cnki.hxsj.2025.0226

Study on the Stability and Sample Preservation of 16 Odor Substances in Environmental Water  GUO Ai-hua，WANG Wei，WANG Chen，LI Kun，WEN Ya (Xicheng District Center for Disease Control and Prevention, Beijing 100120,China)

Abstract： To understand the stability of 16 odorous substances in environmental water and determine optimal preservation conditions,this study investigated their stability in two different matrices (surface water and tap water),as well as the effects of common sampling containers (brown hard glass and brown polyethylene),storage temperatures (20～25 ℃ at room temperature or 0～4 ℃ refrigerated),and commonly used preservatives (ascorbic acid,hydrochloric acid solution,and sodium thiosulfate).Odorous compounds in water samples were detected by solid-phase microextraction-gas chromatography-tandem mass spectrometry.Concentrations of all compounds decreased over time.Terpenoids (2-MIB,GSM) and pyrazines (IPMP,IBMP) were more stable in environmental water than ketones (β-ionone),aldehydes (β-cyclocitral,2,4-HD,2,6-ND),and aromatic heterocycles (indole).After collection,water samples should be stored in ground-mouthed hard brown glass bottles at 0～4 ℃.Polyethylene containers pose a risk of contamination from MTBE and 2,6-dichlorphenol.Compared with room temperature storage,refrigeration slows the loss of target compounds.The stability of 2,4-HD,2,6-ND,β-ionone,and indole was relatively poor in surface water,while 2,4-HD and 2,6-ND were less stable in tap water.Other compounds remained stable for up to 24 h without preservatives.In surface water,2,4-HD,2,6-ND and β-ionone should be stored with hydrochloric acid,and indole with ascorbic acid,with same-day analysis recommended.In tap water,2,4-HD can be preserved for 24 hours with ascorbic acid.The stability of odorous compounds varies by compound and matrix.Therefore,appropriate preservation methods should be applied to ensure accurate measurements.

Key words：environmental water；odorous compounds；stability；sample preservation；SPME-GC-MS/MS

【合成与应用】

以酯键链接的甾体羟肟酸化合物的合成及体外抗肿瘤活性

周涛，刘钦洲，周卉，甘春芳^*

（南宁师范大学化学与材料学院广西天然高分子化学与物理重点实验室，广西南宁  530001）

摘要：分别以胆固醇、去氢表雄酮及孕烯醇酮为原料,通过缩合与水解反应对甾体母核进行结构修饰,并与甾核缀合,设计并合成了一系列通过酯键连接的甾体-羟肟酸新型化合物。采用分步合成策略构建甾体与羟肟酸结构片段,并运用分子杂交方法将两部分缀合,成功制备出多个以酯键相连的甾体-羟肟酸缀合物,同时对实验条件进行了系统优化。在体外抗肿瘤活性筛选中,以SAHA为阳性对照,采用MTT法评估目标化合物的抑制活性。结果显示,N-[(三苯甲基)氨基]-4-氧代丁酸甲酯(4a)和甲基N-[(三苯甲基)氨基]-4-氧代戊酸酯(4b)对SKOV-3肿瘤细胞的增殖抑制效果优于其他测试细胞系。其中,化合物4a对多种肿瘤细胞均表现出一定的抑制活性,尤其对T47D细胞的IC₅₀值为9.23 μmol/L;而化合物4b对HeLa细胞株显示出更强的抑制能力,IC₅₀值低至8.58 μmol/L。进一步通过分子对接研究探讨其作用机制,发现化合物4a可通过多种疏水相互作用表现出更优的结合亲和力,而化合物4b则通过与锌离子结合,在催化抑制方面展现出更高潜力,为开发高效抗肿瘤药物前体化合物提供了新的策略与研究方向。

关键词：甾体；羟肟酸；抗肿瘤药物；合成；分子对接

中图分类号：O621.3           文献标识码：A            文章编号：0258-3283(2026)01-0076-10

DOI：10.13822/j.cnki.hxsj.2025.0246

Synthesis and In-Vitro Antitumor Screening of Ester-Linked Steroid-Hydroxamic Acid Conjugates ZHOU Tao,LIU Qin-zhou,ZHOU Hui,GAN Chun-fang^*（Guangxi Key Laboratory of Natural Polymer Chemistry and Physics,School of Chemistry and Materials,Nanning Normal University,Nanning 530001,China）

Abstract：In this study,cholesterol,dehydroepiandrosterone,and pregnenolone were used as starting materials to design and synthesize a series of novel steroidal-hydroxamic acid conjugates linked via ester bonds.Structural modification of the steroidal core was achieved through condensation and hydrolysis reactions,followed by conjugation with hydroxamic acid fragments.A stepwise synthetic strategy was employed to construct the steroidal and hydroxamic acid fragments,which were subsequently conjugated using a molecular hybridization approach.Multiple steroid-hydroxamic acid conjugates with ester linkages were successfully prepared,and the reaction conditions were systematically optimized.For in vitro antitumor activity screening,the MTT assay was performed with SAHA as a positive control.The results indicated that compounds Methyl N-(tritylamino)-4-oxobutanoate (4a) and Methyl N-(tritylamino)-4-oxopentanoate (4b) exhibited superior antiproliferative activity against SKOV-3 tumor cells compared to other tested cell lines.Compound 4a showed moderate inhibitory activity against several tumor cell lines,with an IC₅₀ value of 9.23 μmol/L against T47D cells,whereas compound 4b demonstrated enhanced potency against the HeLa cell line,achieving an IC₅₀ value as low as 8.58 μmol/L.Molecular docking studies were conducted to further explore the mechanism of action.Compound 4a displayed superior binding affinity through diverse hydrophobic interactions,while 4b exhibited greater potential in catalytic inhibition by coordinating with zinc ions.This research provides a new strategy and direction for the future development of highly effective antitumor drug precursor compounds.

Key words：steroid;hydroxamic acid;antitumor agent;synthesis;molecular docking

可见光诱导氧掺杂氮化碳催化苄基碳氧化合成酮

赵波，谷嘉宁，潘扬，金甲婧，尚积祯，穆兵^*

(湖州师范学院生命科学学院，浙江湖州  313000 )

摘要：芳基酮骨架广泛存在于药物和功能材料中,发展其高效、绿色的合成方法具有重要意义。近年来,以廉价易得的烷基芳烃为原料,通过可见光催化实现苄基碳的直接氧化,为芳基酮的绿色合成提供了新思路。以三聚氰胺为前驱体,通过高温煅烧、热剥离、热氧化制备了氧掺杂氮化碳(O-g-C₃N₄)。在室温下,以二苯甲烷(Ⅰa)为模板底物、O-g-C₃N₄为光催化剂,探究溶剂、催化剂用量、反应时间、光源、反应氛围对二苯甲酮(Ⅱa)产率的影响,筛选最优的反应体系为:在室温、紫光照射、氧气氛围下,以CH₃CN/H₂O(3 mL/3 mL)为溶剂、15 mg O-g-C₃N₄、反应时间为24 h。在筛选最佳的反应条件下,进行底物拓展,以31%～96%产率得到19种芳香酮类化合物,并通过 ¹HNMR、¹³CNMR、MS对其结构进行表征,与目标化合物的结构一致。研究结果表明,该反应体系对芳烃、杂环芳烃苄基碳的氧化均展现较好的底物适用性,并推断苄基碳氧化合成芳香酮可能为单电子转移自由基反应历程。此外,O-g-C₃N₄光催化剂经5次循环利用,氧化产物的产率变化不明显,表明O-g-C₃N₄具有良好的稳定性以及实际应用性。

关键词：光催化；氧掺杂氮化碳；苄基碳的氧化；绿色合成；芳香酮的合成

中图分类号：O62            文献标识码：A             文章编号：0258-3283(2026)01-0086-10

DOI：10.13822/j.cnki.hxsj.2025.0223

Visible Light-Induced Oxygen-Doped Graphitic Carbon Nitride Catalyzed Oxidation of Benzyl Carbons to Ketones  ZHAO Bo, GU Ja-ning, PAN Yang, JIN Jia-jing, SHANG Ji-zhen, MU Bing^* (College of Life Sciences, Huzhou University, Huzhou 313000, China)

Abstract：ryl ketone scaffolds are widely found in pharmaceuticals and functional materials,making the development of efficient and green synthetic methods highly significant.Recently,visible light-mediated direct oxidation of benzylic C―H bonds in readily available alkylarenes has provided a novel approach to the green synthesis of aryl ketones.In this paper,oxygen-doped graphitic carbon nitride (O-g-C₃N₄) was prepared using melamine as the precursor via high-temperature calcination,thermal exfoliation and oxidation.At room temperature,diphenylmethane (Ⅰa) was used as a model substrate and O-g-C₃N₄ as the photocatalyst to systematically investigate the effects of solvent,catalyst loading,reaction time,light source,and reaction temperature on the yield of benzophenone (Ⅱa).The optimized reaction system was identified as follows:CH₃CN/H₂O (3 mL/3 mL) as solvent,15 mg of O-g-C₃N₄,24 h reaction time,room temperature,purple light irradiation,and an oxygen atmosphere.Under the optimized conditions,a broad range of alkylarenes were oxidized to afford 19 aromatic ketones in isolated yields ranging from 31% to 96%.The structures of all products were identified by ¹HNMR,¹³CNMR,and MS,and were consistent with the target compounds.The results demonstrate that this reaction system exhibits good substrate tolerance towards arenes and heteroarenes.Control experiments suggest that the oxidation of benzylic carbons proceeds via a radical-mediated single-electron transfer mechanism.Moreover,the catalyst could be reused for five cycles without significant loss of activity,demonstrating the excellent stability and practical applicability of O-g-C₃N₄.

Key words：photocatalysis; oxygen doped graphitic carbon nitride; oxidation of benzyl carbon; green synthesis; synthesis of aromatic ketone

嘧啶-5-甲醛的新合成工艺

王宇，黄鸿坤，凌春，严兆华^*

(南昌大学 化学化工学院，江西 南昌  330031)

摘要：嘧啶-5-甲醛(1)是合成新型介离子类杀虫剂三氟苯嘧啶的一种原料。报道了嘧啶-5-甲醛的一种新型合成方法。以4,6-二羟基嘧啶(3)为原料,通过Vilsmeier反应首先合成得到了中间体4,6-二氯嘧啶-5-甲醛(2)。中间体化合物2随后在酸催化下和乙醇反应生成相应的缩醛保护产物4,6-二氯-5-(二乙氧基甲基)嘧啶(5c)。化合物5c在钯碳催化下和氢气反应脱去两个氯原子生成了5-(二乙氧基甲基)嘧啶(4c)。最后化合物4c在浓硫酸作用下脱去醛保护基顺利地合成得到了目标产物嘧啶-5-甲醛。4步反应的总产率为75%。详细地考察了不同的缩醛保护基对反应的影响。当使用乙二醇代替乙醇作为化合物2的保护基时,4步反应总产率仅为5%;当使用甲醇代替乙醇作为化合物2的保护基时,4步反应总产率是36%。这些实验结果表明,使用乙醇作为化合物2的保护基,4步反应总产率最高。开发的新型合成方法适合于工业化生产。

关键词：嘧啶-5-甲醛；4,6-二羟基嘧啶；合成；保护基；还原

中图分类号：O62              文献标识码：A             文章编号：0258-3283(2026)01-0094-05

DOI：10.13822/j.cnki.hxsj.2025.0258

A Novel Synthetic Method of Pyrimidine-5-carbaldehyde  WANG Yu, HUANG Hong-kun, LING Chun, YAN Zhaohua^*(College of Chemistry and Chemical Engineering, Nanchang University, Nanchang 330031, China)

Abstract: Pyrimidine-5-carbaldehyde (compound 1) is one of the key starting materials for the synthesis of the novel mesoionic insecticide triflumezopyrim.A novel synthetic method of pyrimidine-5-carbaldehyde is reported.Using 4,6-dihydroxypyrimidine (compound 3) as the starting material,4,6-dichloropyrimidine-5-carbaldehyde (compound 2) was first prepared through the Vilsmeier reaction.The intermediate compound 2 then reacted with ethanol under acid catalysis to form the corresponding acetal-protected product 4,6-dichloro-5-(diethoxymethyl)pyrimidine (compound 5c).Compound 5c was subsequently reduced by H₂ under the catalysis of Pd/C,removing the two chlorine atoms to yield 5-(diethoxymethyl)pyrimidine (compound 4c).Finally,compound 4c was converted to the target product pyrimidine-5-carbaldehyde via deprotection with concentrated H₂SO₄.The overall yield of the four-step reaction was 75%.The effects of different acetal protecting group on the reaction were systematically investigated.When ethylene glycol was used instead of ethanol as the protecting group for intermediate compound 2,the overall yield of the four-step reaction was only 5%;when methanol was used,the yield was 36%.These results indicate that using ethanol as the protecting group for compound 2 provides the highest total yield.The developed protocol was suitable for industrial-scale production.

Key words：pyrimidine-5-carbaldehyde; 4,6-dihydroxypyrimidine; synthesis; protecting group; reduction

1,4-二羰基化合物合成吡咯和喹喔啉的研究

韦琳素，韦美玲，雷禄^*

(百色学院 a. 化学与环境工程学院，b. 广西城市水环境重点实验室，广西 百色  533000)

摘要：吡咯是重要的杂环化合物,它不仅存在于生物药理活性的分子骨架中,还被用于制备电致发光器件导电功能材料。利用布朗斯特酸或路易斯酸等酸催化剂催化伯胺与1,4-二羰基前体反应制备,通过Paal-Knorr反应构建吡咯被认为是最具有吸引力和有效的策略之一。为构建结构新颖的吡咯稠环化合物,在合成吲哚的基础上,发展多取代吡咯化合物的多样性的合成。研究吡咯苯胺与二羰基化合物在酸性条件下的反应,构建结构新颖的吡咯和吡咯稠环衍生物,以拓展含氮杂环衍生物的高效合成。以邻吡咯苯胺和1,4-二羰基化合物(2,5-己二酮)或1,4-酮酯为原料,在一水合对甲苯磺酸存在下进行反应,优化反应条件,如溶剂、反应温度、催化剂用量等反应条件,以中等的产率得到吡咯和吡咯稠环化合物。所得产物均通过 ¹HNMR、¹³CNMR、HRMS进行了表征,新化合物通过单晶X-ray衍射,确定吡咯和吡咯稠环化合物的相对构型。通过控制实验,提出可能反应的机理,对反应中间体进行核磁二维谱确认。发展了一种一水合对甲苯磺酸催化邻吡咯苯胺和1,4-二羰基化合物串联反应的方法,以高化学选择性和区域选择性得到目标化合物,并阐明了二羰基化合物结构对产物选择性的影响。该方法条件温和、收率高,为含氮杂环化合物的合成提供了新策略。

键词：吡咯稠环；1,4-二羰基化合物；分子内环化；串联反应

中图分类号：O62            文献标识码：A             文章编号：0258-3283(2026)01-0099-08

DOI：10.13822/j.cnki.hxsj.2025.0243

Research on the Synthesis of Pyrroles and Quinoxalines from 1,4-Dicarbonyl Compounds  WEI Lin-su, WEI Mei-ling, LEI Lu^*( a. School of Chemical and Environmental Science Engineering, b. Guangxi Key Laboratory of Urban Water Environment, Baise University, Baise 533000, China)

Abstract: Pyrrole is an important heterocyclic compound that not only appears in molecular frameworks with biological and pharmacological activities but is also used in the preparation of conductive functional materials for electroluminescent devices.Among the various synthetic strategies,the Paal-Knorr reaction,using Brønsted acids or Lewis acids to catalyze the reaction between primary amines and 1,4-dicarbonyl precursors,is regarded as one of the most attractive and efficient approach for constructing pyrrole frameworks.To access structurally novel pyrrole-fused ring systems,diverse synthetic routes toward polysubstituted pyrroles has been developed based on the methodologies used for indole construction.This study investigates the reaction of pyrrolylaniline with dicarbonyl compounds under acidic conditions to construct novel pyrrole and pyrrole-fused derivatives,thereby expanding the efficient synthesis of nitrogen-containing heterocyclic derivatives.Using ortho-pyrrolylaniline and 1,4-dicarbonyl compounds (2,5-hexanedione) or 1,4-ketoesters as starting materials,the reactions were carried out in the presence of p-toluenesulfonic acid monohydrate.Optimization of the reaction conditions,including solvent,reaction temperature,and catalyst loading,afforded pyrrole and pyrrole-fused ring compounds in moderate yields.All products were characterized by ¹HNMR,¹³CNMR,and HRMS,while the relative configurations of the new compounds were determined by single-crystal X-ray diffraction.Based on control experiments,a plausible reaction mechanism was proposed,and the reaction intermediates were confirmed by two-dimensional NMR spectroscopy.This work established a p-toluenesulfonic acid monohydrate-catalyzed tandem reaction between ortho-pyrrolylaniline and 1,4-dicarbonyl compounds,delivering target products with high chemoselectivity and regioselectivity.The influence of the structure of the dicarbonyl compounds on product selectivity was also elucidated,providing a new strategy for the synthesis of nitrogen-containing heterocyclic compounds.

Key words：pyrrole-fused rings; 1,4-dicarbonyl compounds; intramolecular cyclization; tandem reaction