Preparation of triaminotriazine-based polyimide-modified electrodes and their use for selective detection of catechin in green tea samples

  • Serap Titretir Duran
  • Nurcan Ayhan
  • Büşra Aksoy
  • Süleyman Köytepe
  • Aziz PaşahanEmail author
Original Paper


An effective electrochemical sensor was developed from triaminotriazine-based polyimide (PI) films as selective membrane for the detection of catechin (CT). Firstly, triaminotriazine-based PI films were synthesized from 2,4,6-triamino-1,3,5-triazine (TAT) and pyromellitic dianhydride by thermal imidization method with different monomer ratios. Structural and morphological of synthesized PI films were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. Prepared polyimide films were used as membrane for the preparation of the modified electrodes. Catechin (CT) selectivity behavior of polyimide-modified Pt electrodes was investigated by means of differential pulse voltammetry (DPV). DPV voltammograms showed that peak currents of the modified electrode increased proportionally with increase in CT concentration. TAT-PI-1/1 sensor showed high selectivity, a high regression coefficient (R value = 0.9982 ), good repeatability (RSD of 2.15%), and limit of detection 0.0152 mM for catechin determination in the presence of multiple interferent species (1 mM coumaric acid, ascorbic acid, gallic acid, lactose, sucrose, fructose, maltose and glucose). Moreover, the TAT-PI-1/1 sensor was employed to determine CT in real sample.


Triaminotriazine-based polyimide film Catechin Selective membrane Sensor 



  1. 1.
    Zanwar A, Badole SL, Shende PS, Hegde MV (2014) Chapter 21. In: Watson RR, Preedy VR (eds) Polyphenols in human health and disease. Academic Press, San Diego, pp 267–271CrossRefGoogle Scholar
  2. 2.
    Wei J, He J, Chen C, Wang X (2015) A catechin-modified carbon paste electrode for electrocatalytic determination of neurotransmitters. Anal Methods 7:5641–5648CrossRefGoogle Scholar
  3. 3.
    Svoboda P, Vlckova H, Novakova LJ (2015) Development and validation of UHPLC-MS/MS method for determination of eight naturally occurring catechin derivatives in various tea samples and the role of matrix effects. Pharm Biomed Anal 114:62–70CrossRefGoogle Scholar
  4. 4.
    Novak I, Seruga M, Komorsky-Lovric S (2010) Characterisation of catechins in green and black teas using square-wave voltammetry and RP-HPLC-ECD. Food Chem 122:1283–1289CrossRefGoogle Scholar
  5. 5.
    Janeiro P, Brett AMO (2004) Catechin electrochemical oxidation mechanisms. Anal Chim Acta 518:109–115CrossRefGoogle Scholar
  6. 6.
    Huo Q, Hao J, Shi R (2013) Determination of catechin by high performance liquid chromatography and ultraviolet spectrophotometer. Asian J Chem 25:8940–8942CrossRefGoogle Scholar
  7. 7.
    Kofink M, Papagiannopoulos M, Galensa R (2007) (-)-catechin in cocoa and chocolate: occurence and analysis of an atypical flavan-3-ol enantiomer. Molecules 12:1274–1288PubMedPubMedCentralCrossRefGoogle Scholar
  8. 8.
    Lunte SM (1987) Structural classification of flavonoids in beverages by liquid chromatography with ultraviolet—visible and electrochemical detection. J Chromatogr B 384:371–382CrossRefGoogle Scholar
  9. 9.
    Lunte SM, Blankenship KD, Read SA (1988) Detection and identification of procyanidins and flavanols in wine by dual-electrode liquid chromatography-electrochemistry. Analyst 113:99–102PubMedCrossRefGoogle Scholar
  10. 10.
    Castaignède V, Durliat H, Comtat M (2003) Amperometric and potentiometric determination of catechin as model of polyphenols in wines. Anal Lett 36:1707–1720CrossRefGoogle Scholar
  11. 11.
    Shumow L, Bodor A (2011) An industry consensus study on an HPLC fluorescence method for the determination of (±)-catechin and (±)-epicatechin in cocoa and chocolate products. Chem Cent J 5:1–7CrossRefGoogle Scholar
  12. 12.
    Donovan JL, Luthria DL, Stremple P, Waterhouse AL (1999) Analysis of (+)-catechin, (-)-epicatechin and their 3’- and 4’-O-methylated analogs. A comparison of sensitive methods. J Chromatogr B Biomed Sci Appl 726:277–283PubMedCrossRefGoogle Scholar
  13. 13.
    Roman MC, Hildreth J, Bannister S (2013) Determination of catechins and caffeine in Camellia sinensis, raw materials, extracts, and dietary supplements by HPLC-UV: single laboratory validation. J AOAC Int 96:933–941PubMedPubMedCentralCrossRefGoogle Scholar
  14. 14.
    Nakagawa K, Miyazama T (1997) Chemiluminescence–high-performance liquid chromatographic determination of tea catechin, (−)-epigallocatechin 3-gallate, at picomole levels in rat and human plasma. Anal Biochem 248:41–49PubMedCrossRefGoogle Scholar
  15. 15.
    Ribeiro GAC, Da Rocha CQ, Tanaka AA, Da Silva S (2018) A fast, direct, and sensitive analysis method for catechin determination in green tea by batch injection analysis with multiple-pulse amperometry (BIA-MPA). Anal Methods 10:2034–2040CrossRefGoogle Scholar
  16. 16.
    Silva AA, Silva LAJ, Munoz RAA, Oliveira AC, Richter EM (2016) Determination of amlodipine and atenolol by batch injection analysis with amperometric detection on boron-doped diamond electrode. Electroanalysis 28:1455–1461CrossRefGoogle Scholar
  17. 17.
    Oliveira GKF, Tormin TF, De RH, Montes O, Richter EM, Munoz RAA (2016) Electrochemical oxidation of astaxanthin on glassy-carbon electrode and its amperometric determination using batch injection analysis (BIA). Electroanalysis 28:2143–2148CrossRefGoogle Scholar
  18. 18.
    Dos Santos Pereira LN, da Silva IS, Araujo TP, Tanaka AA, Angnes L (2016) Fast quantification of α-lipoic acid in biological samples and dietary supplements using batch injection analysis with amperometric detection. Talanta 154:249–254PubMedCrossRefGoogle Scholar
  19. 19.
    Gu W, Wang M, Mao X, Wang Y, Li L, Xia W (2015) A highly sensitive electrochemical sensor based on Cu/Cu2O@carbon nanocomposite structures for hydrazine detection. Anal Methods 7:1313–1320CrossRefGoogle Scholar
  20. 20.
    Abdel-Hamid R, Newair EFJ (2013) Adsorptive stripping voltammetric determination of gallic acid using an electrochemical sensor based on polyepinephrine/glassy carbon electrode and its determination in black tea sample. Electroanal Chem 704:32–37CrossRefGoogle Scholar
  21. 21.
    Gao F, Zheng D, Tanaka H, Zhan F, Yuan X, Gao F, Wang Q (2015) An electrochemical sensor for gallic acid based on Fe2O3/electro-reduced graphene oxide composite: estimation for the antioxidant capacity index of wines. Mater Sci Eng C 57:279–287CrossRefGoogle Scholar
  22. 22.
    Damaceanu MD, Sava I, Constantin CP (2016) The use, design, synthesis, and properties of high performance/high temperature polymers: an overview. Sens Actuators B 234:549–561CrossRefGoogle Scholar
  23. 23.
    Hergenrother PM (2003) The use, design, synthesis, and properties of high performance/high temperature polymers: an overview. High Perform Polym 15:34–35CrossRefGoogle Scholar
  24. 24.
    Chao D, Zhang J, Liu X, Lu X, Wang C, Zhang W, Wei Y (2010) Synthesis of novel poly(amic acid) and polyimide with oligoaniline in the main chain and their thermal, electrochemical, and dielectric properties. Polymer 51:4518–4524CrossRefGoogle Scholar
  25. 25.
    Lau KSY (2014) High-performance polyimides and high temperature resistant polymers, chapter 10. In: Goodman SH, Dodiuk H (eds) Handbook of thermoset plastics, vol 2, 3rd edn. Elsevier, William Andrew Publishing, Boston, pp 297–424CrossRefGoogle Scholar
  26. 26.
    Cai J, Ma L, Niu H, Zhao P, Lian Y, Wang W (2013) Near infrared electrochromic naphthalene-based polyimidescontaining triarylamine: synthesis and electrochemical properties. Electrochim Acta 112:59–67CrossRefGoogle Scholar
  27. 27.
    Hsiao SH, Liou GS, Kung YC, Pan HY, Kuo CH (2009) Electroactive aromatic polyamides and polyimides with adamantyl phenoxy-substituted tripheny-l amine units. Eur Polym J 45:2234–2248CrossRefGoogle Scholar
  28. 28.
    Sadavarte NV, Avadhani CV, Naik PV, Wadgaonkar PP (2010) Regularly alternat-ing poly(amideimide)s containing pendent pentadecyl chains: synthesis and characterization. Eur Polym J 46:1307–1315CrossRefGoogle Scholar
  29. 29.
    Köytepe S, Pasahan A, Ekinci E, Seçkin T (2005) Synthesis, characterization and H2O2-sensing properties of pyrimidine-based hyperbranched polyimides. Eur Polym J 41:121–127CrossRefGoogle Scholar
  30. 30.
    Wessa T, Rapp M, Ache HJ (1999) New immobilization method for SAW-biosensors: covalent attachment of antibodies via CNBr. Biosens Bioelectron 14:93–98PubMedCrossRefGoogle Scholar
  31. 31.
    Lange K, Rapp BE, Rapp M (2008) Surface acoustic wave biosensors: a review. Anal Bioanal Chem 391:1509–1519PubMedCrossRefGoogle Scholar
  32. 32.
    Pasahan A, Köytepe S, Cengiz MA, Seckin T (2013) Maltose-containing polyurethane films: synthesis, characterisation, and their use for determination of dopamine in the presence of the electroactive and nonelectroactive interferents. Int J Polym Mater 62:642–647CrossRefGoogle Scholar
  33. 33.
    Aksoy B, Paşahan A, Güngör Ö, Köytepe S, Seckin T (2016) A novel electrochemical biosensor based on polyimide-boron nitride composite membranes. Int J Polym Mater 66:203–212CrossRefGoogle Scholar
  34. 34.
    Duran ST, Pasahan A, Ayhan N, Güngör Ö, Cengiz MA, Köytepe S (2017) Synthesis, characterization of guar-containing polyurethane films and their non-enzymatic caffeic acid sensor applications. Polym Plast Technol Eng 56:1741–1751CrossRefGoogle Scholar
  35. 35.
    Ekinci E, Köytepe S, Pasahan A, Seckin T (2006) Preparation and characterization of an aromatic polyimide and its use as a selective membrane for H2O2. Turk J Chem 30:277–285Google Scholar
  36. 36.
    Köytepe S, Pasahan A, Ekinci E (2011) Synthesis, characterization of a new organosoluble polyimide and its application in development of glucose biosensor. Polym Plast Technol Eng 50:1239–1246CrossRefGoogle Scholar
  37. 37.
    Pasahan A, Köytepe S, Cengiz MA, Seckin T (2013) Synthesis and characterization of polyurethanes containing glucose for selective determination of epinephrine in the presence of a high concentration of ascorbic acid. Polym Int 62:246–250CrossRefGoogle Scholar
  38. 38.
    Gileadi E, Kirowa-Eisner E, Penciner J (1975) Interfacial electrochemistry: an experimental approach, chapter 10. Addison-Wesley, Reading, pp 311–312Google Scholar
  39. 39.
    Chen Y, Mu D, Chen D (2018) Synthesis, structure and properties of TAP-PMDA hyperbranched polyimides with different terminated groups. J Macromol Sci A 55(8):603–610CrossRefGoogle Scholar
  40. 40.
    Hairul HBH (2017) A study on the estimating DPV surface coverages for chemically modified electrodes. Doctoral Thesis, University of SouthamptonGoogle Scholar
  41. 41.
    Ribeiro GAC, Rocha CQ, Tanaka AA, Silva IS (2018) A fast, direct, and sensitive analysis method for catechin determination in green tea by batch injection analysis with multiple-pulse amperometry (BIA-MPA). Anal Methods 10:2034–2040CrossRefGoogle Scholar
  42. 42.
    Maoela MS, Arotiba OA, Baker PGL, Mabusela WT, Jahed N, Songa EA, Iwuoha EI (2009) Electroanalytical determination of catechin flavonoid in ethyl acetate extracts of medicinal plants. Int J Electrochem Sci 4:1497–1510Google Scholar
  43. 43.
    Masoum S, Behpour M, Azimi F, Motaghedifard MH (2014) Potentiality of chemometric approaches for the determination of (+)-catechin in green tea leaves at the surface of multiwalled carbon nanotube paste electrode. Sens Actuators B Chem 193:582–591CrossRefGoogle Scholar
  44. 44.
    Li Z, Huang D, Tang Z, Deng CJ (2010) Microwave-assisted extraction followed by CE for determination of catechin and epicatechin in green tea. J Sep Sci 33:1079–1084PubMedPubMedCentralGoogle Scholar
  45. 45.
    Fernandes SC, Osório REHM, dos Anjos A, Neves A, Micke GA, Vieira IC (2008) Determination of catechin in green tea using a catechol oxidase biomimetic sensor. J Braz Chem Soc 19:1215–1223CrossRefGoogle Scholar
  46. 46.
    Gottumukkala RVSS, Nadimpalli N, Sukala K, Subbaraju GV (2014) Determination of catechin and epicatechin content in chocolates by high-performance liquid chromatography. Int Sch Res Not 2014:1–5CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Arts and Sciencesİnönü UniversityMalatyaTurkey

Personalised recommendations