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Research progress on analytical methods for the determination of p-phenylenediamine-based rubber antioxidants and their quinone transformation products
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Jiawen CHENG1, *, Jiashun ZHU1, Yajing LIU2, Jing HUA3, Shuang LI4, *
Chinese Journal of Chromatography | 2025, 43(8) : 868 - 880
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Chinese Journal of Chromatography | 2025, 43(8): 868-880
• Reviews •
Research progress on analytical methods for the determination of p-phenylenediamine-based rubber antioxidants and their quinone transformation products
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Jiawen CHENG1, *, Jiashun ZHU1, Yajing LIU2, Jing HUA3, Shuang LI4, *
Affiliations
  • 1. Doublestar Group Co. ,Ltd. ,Qingdao 266400,China
  • 2. Qingdao Eco-environment Monitoring Center of Shandong Province,Qingdao 266003,China
  • 3. School of Polymer Science and Engineering,Qingdao University of Science & Technology,Qingdao 266042,China
  • 4. School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266520,China
Published: 2025-08-08 doi: 10.3724/SP.J.1123.2025.01017
Outline
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p-Phenylenediamine(PPD) compounds are widely used as antidegradants in the rubber industry due to their excellent antioxidant and antiozonant properties. However, increasing environmental concerns have arisen regarding their transformation products, especially quinone derivatives(PPD-Qs), which are formed through oxidative processes under environmental conditions. These compounds have been frequently detected in various matrices, including air, water, sediment, soil, and biota, and have demonstrated significant ecological toxicity even at trace concentration. Accurate quantification of PPDs and PPD-Qs remains a significant analytical challenge due to their low environmental concentrations, high chemical reactivity, and matrix interferences. This review critically evaluates the current state-of-the-art analytical methodologies for the determination of PPDs and PPD-Qs across various environmental compartments. Emphasis is placed on the latest advancements in sample pretreatment techniques and instrumental detection methods that are suitable for complex and heterogeneous matrices. In gaseous and particulate samples, quartz fiber filters, passive samplers, and accelerated solvent extraction(ASE) have been employed for effective compound collection and extraction, with antioxidant protection(e.g., glutathione) used to prevent analyte degradation. solid-phase extraction(SPE) based on hydrophilic-lipophilic balance(HLB) sorbents, as well as salting-out assisted liquid-liquid extraction(SALLE), have achieved high recovery rates and reduced matrix effects. Passive monitoring approaches like diffusive gradients in thin films(DGT) have enabled long-term, time-integrated assessment of waterborne PPD-Qs under varying environmental conditions. For solid or semi-solid matrices such as soil, sediment, and biological tissues, ultrasound-assisted extraction(UAE), gel permeation chromatography(GPC), and modified QuEChERS methods have been widely adopted for high-efficiency extraction and purification. Instrumentally, gas chromatography-mass spectrometry(GC-MS) and liquid chromatography-tandem mass spectrometry(LC-MS/MS) remain the gold standards for sensitive and specific quantification. High-resolution mass spectrometry(HRMS), such as Orbitrap platforms, enables non-targeted screening and structural elucidation of unknown metabolites and degradation products. In addition, emerging techniques such as condensed phase membrane introduction mass spectrometry(CP-MIMS) provide rapid, in situ detection with minimal sample pretreatment, showing great potential for real-time environmental monitoring. Electrochemical sensing platforms based on carbon-based or metal nitride-modified electrodes have also demonstrated promise due to their rapid response, cost-effectiveness, and field-deployable capabilities. However, challenges such as electrode fouling and selectivity limitations remain. In conclusion, this review integrates and evaluates a wide range of analytical approaches for detecting PPDs and PPD-Qs in complex environmental matrices. The comparative analysis of methodologies provides practical insights for optimizing analytical performance and advancing environmental surveillance. Future research should prioritize the development of automated, high-throughput, and green analytical platforms that are adaptable to field monitoring, risk assessment, and regulatory needs for emerging tire-derived contaminants.

p-phenylenediamine  /  rubber antioxidants  /  sample preparation  /  instrumental analysis  /  analytical methods
程嘉雯, 朱家顺, 刘雅静, 华静, 李爽. 对苯二胺类橡胶防老剂及其醌类转化产物分析方法研究进展. 色谱, 2025 , 43 (8) : 868 -880 . DOI: 10.3724/SP.J.1123.2025.01017
Jiawen CHENG, Jiashun ZHU, Yajing LIU, Jing HUA, Shuang LI. Research progress on analytical methods for the determination of p-phenylenediamine-based rubber antioxidants and their quinone transformation products[J]. Chinese Journal of Chromatography, 2025 , 43 (8) : 868 -880 . DOI: 10.3724/SP.J.1123.2025.01017
  • High-Level Talent Support Project of Qingdao University of Technology(20501185)
Year 2025 volume 43 Issue 8
16
6
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Article Info
doi: 10.3724/SP.J.1123.2025.01017
  • Receive Date:2025-01-13
  • Online Date:2026-10-30
  • Published:2025-08-08
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  • Received:2025-01-13
Funding
High-Level Talent Support Project of Qingdao University of Technology(20501185)
Affiliations
    1. Doublestar Group Co. ,Ltd. ,Qingdao 266400,China
    2. Qingdao Eco-environment Monitoring Center of Shandong Province,Qingdao 266003,China
    3. School of Polymer Science and Engineering,Qingdao University of Science & Technology,Qingdao 266042,China
    4. School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266520,China
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表12种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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