Microchimica Acta

, 186:270 | Cite as

A glassy carbon electrode modified with molecularly imprinted poly(aniline boronic acid) coated onto carbon nanotubes for potentiometric sensing of sialic acid

  • Fuhui Huang
  • Bengao Zhu
  • Haochen Zhang
  • Yue Gao
  • Chunmei DingEmail author
  • Hong Tan
  • Jianshu LiEmail author
Original Paper


A potentiometric sensor for sialic acid (SA) was developed based on molecular imprinting technique. The sensor was fabricated by modifying carbon nanotubes (CNT) and an SA-imprinted poly(aniline boronic acid) (PABA) film on a glassy carbon electrode (GCE). The detection strategy capitalizes on the change of electrochemical potential resulting from boronic acid-SA interaction. The imprinted PABA combines the functions of SA-binding boronic acid groups and the imprinting effect, thus endowing it with both chemical and sterical recognition capability. The imprint factor (IF, compared to a non-molecularly imprinted polymer) is 1.74. The sensor can well differentiate SA from its analogs at physiological pH values and has a linear potentiometric response (R2 = 0.998) in 80 μM to 8.2 mM SA concentrations range with a detection limit of 60 μM (at S/N = 3). The sensor was applied to the determination of SA in serum samples and gave recoveries between 93% and 105%.

Graphical abstract

Schematic presentation of the fabrication of a sialic acid (SA) imprinted poly(aniline boronic acid) (PABA)/CNT modified electrode. The electrode can well differentiate SA from its analogs at physiological pH and determine SA in human serum samples with satisfactory recoveries of 93%–105%.


Sialic acid Poly(aniline boronic acid) Carbon nanotubes Physiological pH value Molecularly imprinted polymer Potentiometric response Electrochemical sensor 



The authors are grateful to the financial support by the National Natural Science Foundation of China (51503126 and 21534008) and the kind help of Ms. Fan Yang from Guanghan Chenglin Hospital.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3387_MOESM1_ESM.docx (15.9 mb)
ESM 1 (DOCX 16285 kb)


  1. 1.
    Mahajan VS, Pillai S (2016) Sialic acids and autoimmune disease. Immunol Rev 269:145–161CrossRefGoogle Scholar
  2. 2.
    Fukuda M (1996) Possible roles of tumor-associated carbohydrate antigens. Cancer Res 56:2237–2244PubMedGoogle Scholar
  3. 3.
    Chari SN, Nath N (1984) Sialic acid content and sialidase activity of polymorphonuclear leucocytes in diabetes mellitus. Am J Med Sci 288:18–20CrossRefGoogle Scholar
  4. 4.
    Wang SS, Rymer DL, Good TA (2001) Reduction in cholesterol and sialic acid content protects cells from the toxiceffects of beta-amyloid peptides. J Biol Chem 276:42027–42034CrossRefGoogle Scholar
  5. 5.
    Sankoh S, Thammakhet C, Numnuam A, Limbut W, Kanatharana P, Thavarungkul P (2016) 4-mercaptophenyl- boronicacid functionalized gold nanoparticles for colorimetric sialic acid detection. Biosens Bioelectron 85:743–750CrossRefGoogle Scholar
  6. 6.
    Matsuno K, Suzuki S (2008) Simple fluorimetric method for quantification of sialic acids in glycoproteins. Anal Biochem 375:53–59CrossRefGoogle Scholar
  7. 7.
    Tebani A, Schlemmer D, Imbard A, Rigal O, Porquet D, Benoist JF (2011) Measurement of free and total sialic acid by isotopic dilution liquid chromatography tandem mass spectrometry method. J Chromatogr B Analyt Technol Biomed Life Sci 879:3694–3699CrossRefGoogle Scholar
  8. 8.
    Fatoni A, Numnuam A, Kanatharana P, Limbut W, Thavarungkul P (2014) A conductive porous structuredchitosan-grafted polyaniline cryogel for use as a sialic acid biosensor. Electrochim Acta 130:296–304CrossRefGoogle Scholar
  9. 9.
    James TD, Shinkai S (1996) Saccharide sensing with molecular receptors based on boronic acid. Angew Chem Int Ed 35:1910–1922CrossRefGoogle Scholar
  10. 10.
    Shoji E, Freund MS (2001) Potentiometric sensors based on the inductive effect on the pKa of poly(aniline): a nonenzymatic glucose sensor. J Am Chem Soc 123:3383–3384CrossRefGoogle Scholar
  11. 11.
    Shoji E, Freund MS (2002) Potentiometric saccharide detection based on the pK(a) changes of poly(aniline boronic acid). J Am Chem Soc 124:12486–12493CrossRefGoogle Scholar
  12. 12.
    Zhong X, Bai HJ, Xu JJ, Chen HY, Zhu YH (2010) A reusable interface constructed by 3-aminophenylboronic acid-functionalized multiwalled carbon nanotubes for cell capture, release, and cytosensing. Adv Funct Mater 20:992–999CrossRefGoogle Scholar
  13. 13.
    Matsumoto A, Sato N, Kataoka K, Miyahara Y (2009) Noninvasive sialic acid detection at cell membrane by using phenylboronic acid modified self-assembled monolayer gold electrode. J Am Chem Soc 131:12022–12023CrossRefGoogle Scholar
  14. 14.
    Qian DP, Han FF, Li WB, Bao N, Yu CM, Gu HY (2017) Sensitive determination of sialic acid expression on living cells by using an ITO electrode modified with graphene, gold nanoparticles and thionine for triple signal amplification. Microchim Acta 184:3841–3850CrossRefGoogle Scholar
  15. 15.
    Lorand JP, Edwards JO (1959) Polyol complexes and structure of the benzeneboronate ion. J Org Chem 24:769–774CrossRefGoogle Scholar
  16. 16.
    Deore B, Freund MS (2003) Saccharide imprinting of poly(aniline boronic acid) in the presence of fluoride. Analyst 128:803–806CrossRefGoogle Scholar
  17. 17.
    Otsuka H, Uchimura E, Koshino H, Okano T, Kataoka K (2003) Anomalous binding profile of phenylboronic acid with N-acetylneuraminic acid (Neu5Ac) in aqueous solution with varying pH. J Am Chem Soc 125:3493–3502CrossRefGoogle Scholar
  18. 18.
    Matsumoto A, Cabral H, Sato N, Kataoka K, Miyahara Y (2010) Assessment of tumor metastasis by the direct determination of cell-membrane sialic acid expression. Angew Chem Int Ed 49:5494–5497CrossRefGoogle Scholar
  19. 19.
    Yin DY, Wang SS, He YJ, Liu J, Zhou M, Ouyang J, Liu BR, Chen HY, Liu Z (2015) Surface-enhanced Raman scattering imaging of cancer cells and tissues via sialic acid-imprinted nanotags. Chem Commun 51:17696–17699CrossRefGoogle Scholar
  20. 20.
    Liu RH, Cui QL, Wang C, Wang XY, Yang Y, Li LD (2017) Preparation of sialic acid-imprinted fluorescent conjugated nanoparticles and their application for targeted cancer cell imaging. ACS Appl Mater Interfaces 9:3006–3015CrossRefGoogle Scholar
  21. 21.
    Lv CC, Li HY, Wang HY, Liu Z (2013) Probing the interactions between boronic acids and cis-diol-containingbiomolecules by affinity capillary electrophoresis. Anal Chem 85:2361–2369CrossRefGoogle Scholar
  22. 22.
    Sellergren B, Lepistoe M, Mosbach K (1988) Highly enantioselective and substrate-selective polymers obtained by molecular imprinting utilizing noncovalent interactions. NMR and chromatographic studies on the nature of recognition. J Am Chem Soc 110:5853–5860CrossRefGoogle Scholar
  23. 23.
    Macdiarmid AG, Epstein AJ (1989) The polyanilines: a novel class of conducting polymers. Faraday Discuss Chem Soc 88:317–332CrossRefGoogle Scholar
  24. 24.
    Rick J, Chou TC (2006) Amperometric protein sensor-fabricated as a polypyrrole, poly-aminophenylboronic acid bilayer. Biosens Bioelectron 22:329–335CrossRefGoogle Scholar
  25. 25.
    Baughman RH, Zakhidov AA, Heer WA (2002) Carbon nanotubes-the route toward applications. Science 297:787–792CrossRefGoogle Scholar
  26. 26.
    Shieh YT, Tsai YC, Twu YK (2013) Electrocatalytic behavior and H2O2 detection of carbon nanotube/chitosan nanocomposites prepared via different acidic aqueous solutions. Int J Electrochem Sci 8:831–845Google Scholar
  27. 27.
    Sainz R, Benito AM, Martínez MT, Galindo JF, Sotres J, Baró AM, Corraze B, Chauvet O, Maser WK (2010) Soluble self-aligned carbon nanotube/polyaniline composites. Adv Mater 17:278–281CrossRefGoogle Scholar
  28. 28.
    Takahashi S, Anzai J (2005) Phenylboronic acid monolayer-modified electrodes sensitive to sugars. Langmuir 21:5102–5107CrossRefGoogle Scholar
  29. 29.
    Djanashvili K, Frullano L, Peters JA (2005) Molecular recognition of sialic acid end groups by phenylboronates. Chemistry 11:4010–4018CrossRefGoogle Scholar
  30. 30.
    Yan J, Springsteen G, Deeter S, Wang B (2004) The relationship among pKa, pH, and binding constants in the interactions between boronic acids and diols: it is not as simple as it appears. Tetrahedron 60:11205–11209CrossRefGoogle Scholar
  31. 31.
    Springsteen G, Wang B (2001) Alizarin red S. As a general optical reporter for studying the binding of boronic acids with carbohydrates. Chem Commun 7:1608–1609CrossRefGoogle Scholar
  32. 32.
    Liu TL, Fu B, Chen JC, Yan ZH, Li K (2018) A non-enzymatic electrochemical sensor for detection of sialic acid based on a porphine/graphene oxide modified electrode via indicator displacement assay. Electrochim Acta 269:136–143CrossRefGoogle Scholar
  33. 33.
    Guo X, Liu J, Liu FY, She F, Zheng Q, Tang H, Ma M, Yao SZ (2017) Label-free and sensitive sialic acid biosensor based on organic electrochemical transistors. Sens Actuators B Chem 240:1075–1082CrossRefGoogle Scholar
  34. 34.
    Jayeoye TJ, Cheewasedtham W, Putson C, Rujiralai T (2018) Colorimetric determination of sialic acid based on boronic acid-mediated aggregation of gold nanoparticles. Microchim Acta 185:409–416CrossRefGoogle Scholar
  35. 35.
    Zhou YL, Dong H, Liu LT, Liu J, Xu MT (2014) A novel potentiometric sensor based on a poly(anilineboronic acid)/graphene modified electrode for probing sialic acid through boronic acid-diol recognition. Biosens Bioelectron 60:231–236CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Polymer Science and EngineeringSichuan UniversityChengduChina
  2. 2.State Key Laboratory of Polymer Materials EngineeringSichuan UniversityChengduChina

Personalised recommendations