Advertisement

Microchimica Acta

, Volume 184, Issue 10, pp 4073–4080 | Cite as

A dually functional 4-aminophenylboronic acid dimer for voltammetric detection of hypochlorite, glucose and fructose

  • Murugan Thiruppathi
  • Natarajan Thiyagarajan
  • Manavalan Gopinathan
  • Jen-Lin Chang
  • Jyh-Myng Zen
Original Paper

Abstract

The authors report on the electrochemical process for the modification of a screen printed carbon electrode (SPCE) with an azo-functionalized dimer of 4-amino phenylboronic acid. The dimer is prepared on the surface of the SPCE through the formation of azo bond, and the presence of the dimer is confirmed by cyclic voltammetry, X-ray photoelectron spectroscopy and functional group specific sensing studies. Specifically, this unique dimer-modified electrode possesses dual functionalities (R–N=N-R’ and –B(OH)2) which makes its suitable for selective detection of hypochlorite (i.e., free chlorine) and sugar molecules (demonstrated for glucose and fructose), respectively. The heterogeneous electron transfer rate constant is 7.89 s−1 which indicates a fast electron transfer process at the dimer-modified SPCE. The sensor, operated at a voltage of typically 0.05 V (vs. Ag/AgCl), gives a linear response in the 1 μM to 10 mM hypochlorite concentration range and has a sensitivity of 408.16 μA mM−1 cm−2 at neutral pH values. The catalytic rate constant is 49,872 M s−1 for free chlorine. By using hexacyanoferrate as an electrochemical probe and at a typical working voltage of 0.18 V (vs. Ag/AgCl), the sensor displays a linear response in the 1 to 500 μM fructose and glucose concentration range, with detection limits (for S/N = 3) of 0.24 μM for fructose and 0.36 μM for glucose.

Graphical abstract

Schematic of an electrochemically dimerized 4-aminophenylboronic acid through azo-functionalization route on preanodized screen printed carbon electrode (SPCE*). It was designed for voltammetric sensing of glucose, fructose and hypochlorite using boronic acid and azo moieties, respectively.

Keywords

Screen printed carbon electrode Flow injection Free chlorine Saccharide detection Electrochemical dimerization Fluoride-assisted polymerization 

Notes

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Science and Technology of Taiwan.

Compliance with ethical standards

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

Supplementary material

604_2017_2440_MOESM1_ESM.docx (554 kb)
ESM 1 (DOCX 553 kb)

References

  1. 1.
    Springsteen G, Wang B (2002) A detailed examination of boronic acid–diol complexation. Tetrahedron 58:5291–5300CrossRefGoogle Scholar
  2. 2.
    Tan L, Wang B, Feng H (2013) Comparative studies of graphene oxide and reduced graphene oxide as carbocatalysts for polymerization of 3-aminophenylboronic acid. RSC Adv 3:2561–2565CrossRefGoogle Scholar
  3. 3.
    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
  4. 4.
    Li H, Zhu S, Cheng T, Wang S, Zhu B, Liu X, Zhang H (2016) Binary boronic acid-functionalized attapulgite with high adsorption capacity for selective capture of nucleosides at acidic pH values. Microchim Acta 183:1779–1786CrossRefGoogle Scholar
  5. 5.
    Li M, Zhu W, Marken F, James TD (2015) Electrochemical sensing using boronic acids. Chem Commun 51:14562–14573CrossRefGoogle Scholar
  6. 6.
    Morita K, Hirayama N, Imura H, Yamaguchi A, Teramae N (2011) Grafting of phenylboronic acid on a glassy carbon electrode and its application as a reagentless glucose sensor. J Electroanal Chem 656:192–197CrossRefGoogle Scholar
  7. 7.
    Takahashi S, Anzai J-i (2005) Phenylboronic Acid Monolayer-Modified Electrodes Sensitive to Sugars. Langmuir 21:5102–5107CrossRefGoogle Scholar
  8. 8.
    Zhong M, Teng Y, Pang S, Yan L, Kan X (2015) Pyrrole–phenylboronic acid: A novel monomer for dopamine recognition and detection based on imprinted electrochemical sensor. Biosens Bioelectron 64:212–218CrossRefGoogle Scholar
  9. 9.
    Çiftçi H, Oztekin Y, Tamer U, Ramanavicine A, Ramanavicius A (2014) Development of poly(3-aminophenylboronic acid) modified graphite rod electrode suitable for fluoride determination. Talanta 126:202–207CrossRefGoogle Scholar
  10. 10.
    Nicolas M, Fabre B, Marchand G, Simonet J (2000) New Boronic-Acid- and Boronate-Substituted Aromatic Compounds as Precursors of Fluoride-Responsive Conjugated Polymer Films. Eur J Org Chem 2000:1703–1710CrossRefGoogle Scholar
  11. 11.
    Wu S, Han T, Guo J, Cheng Y (2015) Poly(3-aminophenylboronic acid)-reduced graphene oxide nanocomposite modified electrode for ultrasensitive electrochemical detection of fluoride with a wide response range. Sens Actuators B Chem 220:1305–1310CrossRefGoogle Scholar
  12. 12.
    Wang Z, Shang K, Dong J, Cheng Z, Ai S (2012) Electrochemical immunoassay for subgroup J of avian leukosis viruses using a glassy carbon electrode modified with a film of poly (3-thiophene boronic acid), gold nanoparticles, graphene and immobilized antibody. Microchim Acta 179:227–234CrossRefGoogle Scholar
  13. 13.
    Badhulika S, Tlili C, Mulchandani A (2014) Poly(3-aminophenylboronic acid)-functionalized carbon nanotubes-based chemiresistive sensors for detection of sugars. Analyst 139:3077–3082CrossRefGoogle Scholar
  14. 14.
    Lapinsonnière L, Picot M, Poriel C, Barrière F (2013) Phenylboronic Acid Modified Anodes Promote Faster Biofilm Adhesion and Increase Microbial Fuel Cell Performances. Electroanalysis 25:601–605CrossRefGoogle Scholar
  15. 15.
    Lawrence K, Nishimura T, Haffenden P, Mitchels JM, Sakurai K, Fossey JS, Bull SD, James TD, Marken F (2013) Pyrene-anchored boronic acid receptors on carbon nanoparticle supports: fluxionality and pore effects. New J Chem 37:1883–1888CrossRefGoogle Scholar
  16. 16.
    Hong S, Lee LYS, So M-H, Wong K-Y (2013) A Dopamine Electrochemical Sensor Based on Molecularly Imprinted Poly(acrylamidophenylboronic acid) Film. Electroanalysis 25:1085–1094CrossRefGoogle Scholar
  17. 17.
    Senthilkumar K, Zen J-M (2014) Free chlorine detection based on EC’ mechanism at an electroactive polymelamine-modified electrode. Electrochem Commun 46:87–90CrossRefGoogle Scholar
  18. 18.
    Wang Q, Kaminska I, Niedziolka-Jonsson J, Opallo M, Li M, Boukherroub R, Szunerits S (2013) Sensitive sugar detection using 4-aminophenylboronic acid modified graphene. Biosens Bioelectron 50:331–337CrossRefGoogle Scholar
  19. 19.
    Qiang Z, Adams CD (2004) Determination of Monochloramine Formation Rate Constants with Stopped-Flow Spectrophotometry. Environ Sci Technol 38:1435–1444CrossRefGoogle Scholar
  20. 20.
    Thiruppathi M, Thiyagarajan N, Gopinathan M, Zen J-M (2016) Role of defect sites and oxygen functionalities on preanodized screen printed carbon electrode for adsorption and oxidation of polyaromatic hydrocarbons. Electrochem Commun 69:15–18CrossRefGoogle Scholar
  21. 21.
    Liu G, Luais E, Gooding JJ (2011) The Fabrication of Stable Gold Nanoparticle-Modified Interfaces for Electrochemistry. Langmuir 27:4176–4183CrossRefGoogle Scholar
  22. 22.
    Wong C-S, Chen Y-D, Chang J-L, Zen J-M (2015) Biomolecule-free, selective detection of clenbuterol based on disposable screen-printed carbon electrode. Electrochem Commun 60:163–167CrossRefGoogle Scholar
  23. 23.
    Xu LQ, Liu YL, Neoh K-G, Kang E-T, Fu GD (2011) Reduction of Graphene Oxide by Aniline with Its Concomitant Oxidative Polymerization. Macromol Rapid Commun 32:684–688CrossRefGoogle Scholar
  24. 24.
    Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem Interfacial Electrochem 101:19–28CrossRefGoogle Scholar
  25. 25.
    White GC (1986) Handbook of Chlorination, 2nd edn. Van Nostrand Reinhold Company Inc, New YorkGoogle Scholar
  26. 26.
    Wilcox MH, Fawley WN, Wigglesworth N, Parnell P, Verity P, Freeman J (2003) Comparison of the effect of detergent versus hypochlorite cleaning on environmental contamination and incidence of Clostridium difficile infection. J Hosp Infect 54:109–114CrossRefGoogle Scholar
  27. 27.
    World Health Organization (2006) Guidelines for safe recreational water environments. Volume 2: Swimming pools and similar environments. World Health Organization, GenevaGoogle Scholar
  28. 28.
    Compton RG, Banks CE (2010) Understanding voltammetry. Imperial college Press, LondonCrossRefGoogle Scholar
  29. 29.
    Salazar P, Martín M, García-García FJ, González-Mora JL, González-Elipe AR (2015) A novel and improved surfactant-modified Prussian Blue electrode for amperometric detection of free chlorine in water. Sens Actuators B Chem 213:116–123CrossRefGoogle Scholar
  30. 30.
    Pathiratne K, Skandaraja S, Jayasena E (2009) Linear sweep voltammetric determination of free chlorine in waters using graphite working electrodes. J Natl Sci Found Sri 36:25–31Google Scholar
  31. 31.
    Tsai T-H, Lin K-C, Chen S-M (2011) Electrochemical synthesis of poly (3, 4-ethylenedioxythiophene) and gold nanocomposite and its application for hypochlorite sensor. Int J Electrochem Sci 6:2672–2687Google Scholar
  32. 32.
    Hallaj T, Amjadi M, Manzoori JL, Shokri R (2015) Chemiluminescence reaction of glucose-derived graphene quantum dots with hypochlorite, and its application to the determination of free chlorine. Microchim Acta 182:789–796CrossRefGoogle Scholar
  33. 33.
    Lin Y, Yao B, Huang T, Zhang S, Cao X, Weng W (2016) Selective determination of free dissolved chlorine using nitrogen-doped carbon dots as a fluorescent probe. Microchim Acta 183:2221–2227CrossRefGoogle Scholar
  34. 34.
    Yu H, Zheng L (2016) Manganese dioxide nanosheets as an optical probe for photometric determination of free chlorine. Microchim Acta 183:2229–2234CrossRefGoogle Scholar
  35. 35.
    Moberg L, Karlberg B (2000) An improved N,N′-diethyl-p-phenylenediamine (DPD) method for the determination of free chlorine based on multiple wavelength detection. Anal Chim Acta 407:127–133CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria 2017

Authors and Affiliations

  • Murugan Thiruppathi
    • 1
  • Natarajan Thiyagarajan
    • 1
  • Manavalan Gopinathan
    • 1
  • Jen-Lin Chang
    • 1
  • Jyh-Myng Zen
    • 1
  1. 1.Department of ChemistryNational Chung Hsing UniversityTaichungTaiwan

Personalised recommendations