Citation: Qiang Fang, Yingbo Lu, Jianying Huang, Cheng Zhang, Jing Wu, Shijun Li. An electrochemical immunosensor based on an antibody-ferrocene-functionalized covalent organic framework[J]. Chinese Chemical Letters, ;2026, 37(2): 111218. doi: 10.1016/j.cclet.2025.111218 shu

An electrochemical immunosensor based on an antibody-ferrocene-functionalized covalent organic framework

Qiang Fang ^{a, b} ,
Yingbo Lu ^c ,
Jianying Huang ^b ,
Cheng Zhang ^{a, *,} ,
Jing Wu ^c ,
Shijun Li ^{c, *,}

a.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
b.
College of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310018, China
c.
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China

czhang@zjut.edu.cn

l_shijun@hznu.edu.cn

Received Date: 16 January 2025
Revised Date: 9 April 2025
Accepted Date: 15 April 2025
Available Online: 15 April 2025

Figures(6)

High-sensitive quantitative determination of alpha-fetoprotein (AFP) is of crucial importance for early clinical diagnosis of cancers. Herein, an AuNPs-free electrochemical immunosensor (Ab1-Fc-COF) was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody (Ab1) and ferrocene (Fc), and used for electrochemical detection of AFP. Due to the small, homogeneous pore size of the COF, Ab1 with a big size was immobilized on the surface of the COF, while Fc with a small size was covalently modified both on the surface and in the pores of COF. The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers. Meanwhile, the enriched Fc molecules not only improved the conductivity of the COF, but also effectively transferred and amplified the electrochemical signal. This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL (S/N of 3:1) and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations. Furthermore, this immunosensor showed excellent selectivity, stability and reproducibility in the testing of real samples. This study presents an innovative prototype for construction of a precious metal-free, antibody-directly-immobilized, simple and stable electrochemical immunoprobe.
- Covalent organic frameworks,
- Post-functionalization,
- Ferrocene,
- Electrochemical immunosensors,
- Alpha-fetoprotein
1. [1]
  D. Crosby, S. Bhatia, K.M. Brindle, et al., Science 375 (2022) eaay9040. doi: 10.1126/science.aay9040
2. [2]
  N. Tayob, F. Kanwal, A. Alsarraj, et al., Clin. Gastroenterol. Hepatol. 21 (2023) 415–423. doi: 10.1016/j.cgh.2022.01.047
3. [3]
  Z.H. Yang, J. Yin, L. Xin, et al., Chin. Chem. Lett. 35 (2024) 109558. doi: 10.1016/j.cclet.2024.109558
4. [4]
  H. Moulahoum, F. Ghorbanizamani, S. Timur, Anal. Chim. Acta 1306 (2024) 342617. doi: 10.1016/j.aca.2024.342617
5. [5]
  S. Tang, J. Cai, K. Zhou, Anal. Methods 16 (2024) 6443–6450. doi: 10.1039/d4ay01410c
6. [6]
  C. Zheng, P. Dai, H. You, et al., Anal. Sci. 40 (2024) 1239–1248. doi: 10.1007/s44211-024-00553-3
7. [7]
  Z. Song, Q. Hao, B. Li, et al., Chin. Chem. Lett. 36 (2025) 109834. doi: 10.1016/j.cclet.2024.109834
8. [8]
  B. Cong, W. Liang, W. Lai, et al., Bioelectrochemistry 156 (2024) 108626. doi: 10.1016/j.bioelechem.2023.108626
9. [9]
  H. Wu, X. Yang, Bioelectrochemistry 160 (2024) 108773. doi: 10.1016/j.bioelechem.2024.108773
10. [10]
  W. Chen, X. Zhang, M. Chi, et al., Anal. Chim. Acta 1330 (2024) 343281. doi: 10.1016/j.aca.2024.343281
11. [11]
  Z. Shang, T. Su, D. Jin, et al., Biosens. Bioelectron. 230 (2023) 115245. doi: 10.1016/j.bios.2023.115245
12. [12]
  F.B. Kayani, S. Rafique, R. Akram, et al., Nanotechnology 34 (2023) 265501. doi: 10.1088/1361-6528/acc8d8
13. [13]
  V.N. Palakollu, Y.V.M. Reddy, M.I. Shekh, et al., Clin. Chim. Acta 557 (2024) 117882. doi: 10.1016/j.cca.2024.117882
14. [14]
  K. Malecka-Baturo, I. Grabowska, Talanta 281 (2025) 126870. doi: 10.1016/j.talanta.2024.126870
15. [15]
  S. Madhurantakam, B.E. David, A. Naqvi, et al., Anal. Methods 16 (2024) 6615–6633. doi: 10.1039/d4ay01049c
16. [16]
  C.W. Shan, Z. Chen, G.C. Han, et al., Talanta 271 (2024) 125638. doi: 10.1016/j.talanta.2024.125638
17. [17]
  D. Liang, Y. Wang, K. Qian, Interdiscip. Med. 1 (2023) e20230020. doi: 10.1002/INMD.20230020
18. [18]
  A.V.P. Patil, Y.S. Chuang, C. Li, et al., Biosensors 13 (2023) 125. doi: 10.3390/bios13010125
19. [19]
  Y. Zhu, Z. Cheng, X. Wang, et al., Biosens. Bioelectron. 274 (2025) 117222. doi: 10.1016/j.bios.2025.117222
20. [20]
  M.S. Raziyan, A. Palevicius, G. Janusas, J. Electrochem. Soc. 171 (2024) 077510. doi: 10.1149/1945-7111/ad586f
21. [21]
  J. Li, G. Chen, C. Chen, et al., Chin. Chem. Lett. 36 (2025) 109760. doi: 10.1016/j.cclet.2024.109760
22. [22]
  H. Li, Z. Zhou, T. Ma, et al., J. Am. Chem. Soc. 146 (2024) 35486–35492. doi: 10.1021/jacs.4c14971
23. [23]
  X. Cao, Y. Jin, H. Wang, et al., Chin. Chem. Lett. 35 (2024) 109201. doi: 10.1016/j.cclet.2023.109201
24. [24]
  Z. Alsudairy, N. Brown, A. Campbell, et al., Mater. Chem. Front. 7 (2023) 3298–3331. doi: 10.1039/d3qm00188a
25. [25]
  Y. Chen, S. Huang, L. Xia, et al., Anal. Chem. 96 (2024) 1380–1389. doi: 10.1021/acs.analchem.3c05227
26. [26]
  C. Liu, C. Jia, S.X. Gan, et al., Chin. Chem. Lett. 35 (2024) 109750. doi: 10.1016/j.cclet.2024.109750
27. [27]
  W. Feng, C. Gao, R. Xu, et al., Coord. Chem. Rev. 515 (2024) 215965. doi: 10.1016/j.ccr.2024.215965
28. [28]
  Y. Shi, J. Yang, F. Gao, et al., ACS Nano 17 (2023) 1879–1905. doi: 10.1021/acsnano.2c11346
29. [29]
  F. Hernández-García, G.A. Álvarez-Romero, R. Colorado-Peralta, et al., J. Electrochem. Soc. 171 (2024) 077521. doi: 10.1149/1945-7111/ad659b
30. [30]
  R. Xue, Y.S. Liu, S.L. Huang, et al., ACS Sens. 8 (2023) 2124–2148. doi: 10.1021/acssensors.3c00269
31. [31]
  E. Martínez-Periñán, M. Martínez-Fernández, J.L. Segura, et al., Sensors 22 (2022) 4758. doi: 10.3390/s22134758
32. [32]
  C. Hou, J. Liu, S. Zhang, et al., Sens. Actuators B 417 (2024) 136221. doi: 10.1016/j.snb.2024.136221
33. [33]
  S.H. Wen, H. Zhang, S. Yu, et al., Anal. Chem. 95 (2023) 14914–14924. doi: 10.1021/acs.analchem.3c02171
34. [34]
  S. Liu, Q. Zhang, X. Zhang, et al., Anal. Chem. 96 (2024) 10408–10415. doi: 10.1021/acs.analchem.4c01604
35. [35]
  X. Peng, J. Zhu, Z. Wu, et al., Sens. Actuators B 392 (2023) 134074. doi: 10.1016/j.snb.2023.134074
36. [36]
  M. Wang, Y. Pan, S. Wu, et al., Biosens. Bioelectron. 169 (2020) 112638. doi: 10.1016/j.bios.2020.112638
37. [37]
  J. Zheng, H. Zhao, G. Ning, et al., Talanta 233 (2021) 122520. doi: 10.1016/j.talanta.2021.122520
38. [38]
  H. Liang, H. Xu, Y. Zhao, et al., Biosens. Bioelectron. 144 (2019) 111691. doi: 10.1016/j.bios.2019.111691
39. [39]
  H. Liang, Y. Luo, Y. Li, et al., Anal. Chem. 94 (2022) 5352–5358. doi: 10.1021/acs.analchem.1c05426
40. [40]
  H. Liang, Y. Luo, Y. Xiao, et al., Chem. Eng. J. 460 (2023) 141740. doi: 10.1016/j.cej.2023.141740
41. [41]
  H. Beitollahi, M.A. Khalilzadeh, S. Tajik, et al., ACS Omega 5 (2020) 2049–2059. doi: 10.1021/acsomega.9b03788
42. [42]
  G. Roy, R. Gupta, S.R. Sahoo, et al., Coord. Chem. Rev. 473 (2022) 214816. doi: 10.1016/j.ccr.2022.214816
43. [43]
  M. Dervisevic, E. Dervisevic, M. Senel, et al., Enzyme. Microb. Tech. 102 (2017) 53–59. doi: 10.1016/j.enzmictec.2017.04.002
44. [44]
  R.E. Ruther, Q. Cui, R.J. Hamers, et al., J. Am. Chem. Soc. 135 (2013) 5751–5761. doi: 10.1021/ja312680p
45. [45]
  Z. Song, J. Song, F. Gao, et al., Sens. Actuators B 368 (2022) 132205. doi: 10.1016/j.snb.2022.132205
46. [46]
  S. Feng, Y. Xue, J. Huang, et al., Anal. Chem. 94 (2022) 16945–16952. doi: 10.1021/acs.analchem.2c04482
47. [47]
  J.Y. Yue, L. Wang, Y. Ma, et al., Dalton Trans. 48 (2019) 17763–17769. doi: 10.1039/c9dt04175c
48. [48]
  S. Kandambeth, A. Mallick, B. Lukose, et al., J. Am. Chem. Soc. 134 (2012) 19524–19527. doi: 10.1021/ja308278w
49. [49]
  B.P. Biswal, S. Chandra, S. Kandambeth, et al., J. Am. Chem. Soc. 135 (2013) 5328–5331. doi: 10.1021/ja4017842
50. [50]
  T. Feng, X. Qiao, H. Wang, et al., Biosens. Bioelectron. 79 (2016) 48–54.
51. [51]
  Y. Cao, R. Wu, Y.Y. Gao, et al., Nano Micro Lett. 16 (2024) 37. doi: 10.13168/agg.2024.0004
1. [1]
  Jiaqi Ma , Lan Li , Yiming Zhang , Jinjie Qian , Xusheng Wang . Covalent organic frameworks: Synthesis, structures, characterizations and progress of photocatalytic reduction of CO2. Chinese Journal of Structural Chemistry, 2024, 43(12): 100466-100466. doi: 10.1016/j.cjsc.2024.100466
2. [2]
  Xinrui Chen , Wenjian Huang , Xiaoyang Zhao , Songyao Zhang , Xinrui Miao . Structural regulation of alkynyl-based covalent organic frameworks for multi-stimulus fluorescence sensing. Chinese Journal of Structural Chemistry, 2025, 44(7): 100604-100604. doi: 10.1016/j.cjsc.2025.100604
3. [3]
  Weixu Li , Yuexin Wang , Lin Li , Xinyi Huang , Mengdi Liu , Bo Gui , Xianjun Lang , Cheng Wang . Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide. Chinese Journal of Structural Chemistry, 2024, 43(7): 100299-100299. doi: 10.1016/j.cjsc.2024.100299
4. [4]
  Yuting Wu , Haifeng Lv , Xiaojun Wu . Design of two-dimensional porous covalent organic framework semiconductors for visible-light-driven overall water splitting: A theoretical perspective. Chinese Journal of Structural Chemistry, 2024, 43(11): 100375-100375. doi: 10.1016/j.cjsc.2024.100375
5. [5]
  Lina Xie , Xiaohe Zhang , Xiaobo Wang , Zhen Zhang , Tianqi Nie , Jun Wu , Xiaojun Xu . Multifunctional GelMA hydrogel doped with spermidine-ferrocene polymeric nanoparticles for accelerative diabetic wound healing. Chinese Chemical Letters, 2025, 36(11): 110848-. doi: 10.1016/j.cclet.2025.110848
6. [6]
  Deshuai Zhen , Chunlin Liu , Qiuhui Deng , Shaoqi Zhang , Ningman Yuan , Le Li , Yu Liu . A review of covalent organic frameworks for metal ion fluorescence sensing. Chinese Chemical Letters, 2024, 35(8): 109249-. doi: 10.1016/j.cclet.2023.109249
7. [7]
  Yujie Wang , Haoran Wang , Yanni Liu , Manhua Peng , Hongwei Fan , Hong Meng . A comprehensive review on the scalable and sustainable synthesis of covalent organic frameworks. Chinese Chemical Letters, 2025, 36(8): 110189-. doi: 10.1016/j.cclet.2024.110189
8. [8]
  Qi Li , Minqiao Liang , Huifen Zhuang , Zhengyang Chen , Yuxiang Jiang , Xiaofei Chen , Yifa Chen , Ya-Qian Lan . Underscoring the polyimide-linkage in covalent organic frameworks and related applications. Chinese Chemical Letters, 2026, 37(2): 111593-. doi: 10.1016/j.cclet.2025.111593
9. [9]
  Liying Ou , Zhenluan Xue , Bo Li , Zhiwei Jin , Jiaochan Zhong , Lixia Yang , Penghui Shao , Shenglian Luo . Nitrogen-containing linkage-bonds in covalent organic frameworks: Synthesis and applications. Chinese Chemical Letters, 2025, 36(6): 110294-. doi: 10.1016/j.cclet.2024.110294
10. [10]
  Bo Li , Yuanzhe Cheng , Xuyang Ma , Dongxu Zhao , Yang Zhang , Yongxing Sun , Jia Chen , Li Wu , Liang Zhao , Hongdeng Qiu , Yujian He . Facile and scale-up synthesis of cyano-functionalized covalent organic frameworks for selective gold recovery. Chinese Chemical Letters, 2026, 37(1): 111134-. doi: 10.1016/j.cclet.2025.111134
11. [11]
  Shiyan Ai , Yaning Xu , Hui Zhou , Ziwei Cui , Tiantian Wu , Dan Tian . Superelastic and ultralight covalent organic framework composite aerogels modified with different functional groups for ultrafast adsorbing organic pollutants in water. Chinese Chemical Letters, 2025, 36(10): 110761-. doi: 10.1016/j.cclet.2024.110761
12. [12]
  Guorong Li , Yijing Wu , Chao Zhong , Yixin Yang , Zian Lin . Predesigned covalent organic framework with sulfur coordination: Anchoring Au nanoparticles for sensitive colorimetric detection of Hg(Ⅱ). Chinese Chemical Letters, 2024, 35(5): 108904-. doi: 10.1016/j.cclet.2023.108904
13. [13]
  Yue Qian , Zhoujia Liu , Haixin Song , Ruize Yin , Hanni Yang , Siyang Li , Weiwei Xiong , Saisai Yuan , Junhao Zhang , Huan Pang . Imide-based covalent organic framework with excellent cyclability as an anode material for lithium-ion battery. Chinese Chemical Letters, 2024, 35(6): 108785-. doi: 10.1016/j.cclet.2023.108785
14. [14]
  Ming Yue , Yi-Rong Wang , Jia-Yong Weng , Jia-Li Zhang , Da-Yu Chi , Mingjin Shi , Xiao-Gang Hu , Yifa Chen , Shun-Li Li , Ya-Qian Lan . Multi-metal porous crystalline materials for electrocatalysis applications. Chinese Chemical Letters, 2025, 36(6): 110049-. doi: 10.1016/j.cclet.2024.110049
15. [15]
  Lu Zhang , Baohua Wang , Wei Yang , Lunan Ju , Zihan Fu , Lei Zhao , Yunqi Jiang , Hongyan Wang , Xiansheng Wang , Cong Lyu . CoOOH@COFs S−scheme heterojunction for efficient triclosan degradation in photocatalytic-peroxymonosulfate activation system: Enhanced interfacial electron transfer mechanism. Chinese Chemical Letters, 2026, 37(1): 111142-. doi: 10.1016/j.cclet.2025.111142
16. [16]
  Guilan He , Yaofeng Yuan . 手性二茂铁双膦配体Xyliphos的合成及应用. University Chemistry, 2025, 40(8): 130-137. doi: 10.12461/PKU.DXHX202409122
17. [17]
  Dafa Chen , Haiping Xia . From Pollutant to Metal-Centred Annulene: The Transformation Journey of a Little Osmium Atom. University Chemistry, 2025, 40(10): 156-160. doi: 10.12461/PKU.DXHX202508094
18. [18]
  Yunyu Zhao , Chuntao Yang , Yingjian Yu . A review on covalent organic frameworks for rechargeable zinc-ion batteries. Chinese Chemical Letters, 2024, 35(7): 108865-. doi: 10.1016/j.cclet.2023.108865
19. [19]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
20. [20]
  Xue-Zhi Wang , Yi-Tong Liu , Chuang-Wei Zhou , Bei Wang , Dong Luo , Mo Xie , Meng-Ying Sun , Yong-Liang Huang , Jie Luo , Yan Wu , Shuixing Zhang , Xiao-Ping Zhou , Dan Li . Amplified circularly polarized luminescence of chiral metal-organic frameworks via post-synthetic installing pillars. Chinese Chemical Letters, 2024, 35(10): 109380-. doi: 10.1016/j.cclet.2023.109380

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(11)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142