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Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes

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Abstract

Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.

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References

  1. Cook MJ (1999) Phthalocyanine thin films. Pure Appl Chem 71:2145

    Article  CAS  Google Scholar 

  2. Li Z, Lieberman M (2001) XPS and SERS study of silicon phthalocyanine monolayer on gold surface. Langmuir 17:4887

    Article  CAS  Google Scholar 

  3. Revell DJ, Chambrier I, Cook MJ, Russel DA (2000) Formation and spectroscopic characterisation of self-assembled phthalocyanine monolayers. J Mater Chem 10:31

    Article  CAS  Google Scholar 

  4. Goux A, Bedioui F, Robbiola L, Pontie MM (2003) Nickel Tetra-amino phthalocyanine based films for the electrocatalytic activation of dopamine. Electroanalysis 15:969

    Article  CAS  Google Scholar 

  5. Mashazi PN, Ozoemena KI, Nyokong T (2007) Tetracarboxylic acid cobalt phthalocyanine SAM on gold: Potential applications as amperometric sensor for H2O2 and fabrication of glucose biosensor. Electrochim Acta 52:177

    Article  Google Scholar 

  6. Laforgue A, Addou T, Belanger D (2005) Characterization of the deposition of organic molecules at the surface of gold by the electrochemical reduction of aryl diazonium cations. Langmuir 21:6855

    Article  CAS  Google Scholar 

  7. Liu G, Bocking T, Gooding JJ (2007) Diazonium: stable monolayers on gold electrodes for sensing applications. J Electroanal Chem 600:335

    Article  CAS  Google Scholar 

  8. Matemadombo F, Westbroek P, Nyokong T (2007) Electroanalysis of thiocyanate using a novel glassy carbon electrode modified by aryl radicals and cobalt tetracarboxy phthalocyanine. Electrochim Acta 53:480

    Article  CAS  Google Scholar 

  9. Kariuki JK, McDermott MT (1999) Nucleation and growth of functionalized aryl films on graphite electrodes. Langmuir 15:6534

    Article  CAS  Google Scholar 

  10. Saby C, Ortiz B, Champagne GY, Belanger D (1997) Electrochemical modification of glassy carbon electrode using aromatic diazonium salts. 1. Blocking effect of 4-Nitrophenyl and 4-Carboxyphenyl Groups. Langmuir 13:6805

    Article  CAS  Google Scholar 

  11. Brooksby PA, Downard AJ (2004) Electrochemical and atomic force microscopy study of carbon surface modification via diazonium reduction in aqueous and acetonitrile solutions. Langmuir 20:5035

    Article  Google Scholar 

  12. Liu G, Paddon-Row MN, Gooding JJ (2007) A molecular wire modified glassy carbon electrode for achieving direct electron transfer to native glucose oxidase. Electrochem Comm 9:2218

    Article  CAS  Google Scholar 

  13. Kariuki JK, McDermott MT (2001) Formation of multilayers on glassy carbon electrodes via the reduction of diazonium salts. Langmuir 17:5947

    Article  CAS  Google Scholar 

  14. Radi A-E, Munoz-Berbel X, Cortina-Piug M, Marty J-L (2009) An electrochemical immunosensor for ochratoxin A based on immobilization of antibodies on diazonium-functionalized gold electrode. Electrochim Acta 54:2180

    Article  CAS  Google Scholar 

  15. Griveau S, Mercier D, Vautrin-UI V, Chausse A (2007) Electrochemical grafting by reduction of 4-aminoethylbenzezediazonium salt: Applications to the immobilization of biomolecules. Electrochem Comm 9:2768

    Article  CAS  Google Scholar 

  16. Achar BN, Lokesh KS (2004) Studies on tetra-amine phthalocyanines. J Organometal Chem 689:3357

    Article  CAS  Google Scholar 

  17. Obirai J, Nyokong T (2005) Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes. Electrochim Acta 50:5427

    Article  CAS  Google Scholar 

  18. Song S-N, Li D-M, Zhuang C-F, Ding H, Song W-B, Ciu L-F, Cao G-Z, Liu G-F (2007) Syntheses and characterization of molybdenum/zinc porphyrin dimers bridged by aromatic linkers. Eur J Inorg Chem 1844

  19. Anderson HL (1999) Building molecular wires from the colours of life: conjugated porphyrin oligomers. Chem Comm 2323

  20. Delamar M, Hitmi R, Pinson J, Saveant JM (1992) Covalent modification of carbon surfaces by grafting of functionalized aryl radicals produced from electrochemical reduction of diazonium salts. J Am Chem Soc 114:5883

    Article  CAS  Google Scholar 

  21. Anariba F, DuVall SH, McCreery RL (2003) Mono- and multilayer formation by diazonium reduction on carbon surfaces monitored with atomic force microscopy “scratching”. Anal Chem 17:3837

    Article  Google Scholar 

  22. Mashazi PN, Westbroek P, Ozoemena KI, Nyokong T (2007) Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode. Electrochim Acta 53:1858

    Article  CAS  Google Scholar 

  23. Griveau S, Pavez J, Zagal JH, Bedoui F (2001) Electro-oxidation of 2-mercaptoethanol on adsorbed monomeric and electropolymerized cobalt tetra-aminophthalocyanine films. Effect of film thickness. J Electroanal Chem 497: 75.

    Google Scholar 

  24. Obirai J, Nyokong T (2004) Electrochemical studies of manganese tetra-amino phthalocyanine monomer and polymer. Electrochim Acta 49:1417

    CAS  Google Scholar 

  25. Mashazi P, Chamutorwa C, Limson J, Nyokong T (2010) Applications of polymerized metal tetra-amino phthalocyanines towards hydrogen peroxide detection. J Porphyrins Phthalocyanines 14:252

    Article  CAS  Google Scholar 

  26. Finklea HO (1996) In: Bard AJ, Rubinstein I (eds) Electroanalytical chemistry. volume 19. Dekker, New York. pp 109–335

  27. Somashekarappa MP, Keshavayya J, Sampath S (2002) Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization. Pure Appl Chem 74:1609

    Article  CAS  Google Scholar 

  28. Ozoemena KI, Nyokong T (2006) Comparative electrochemistry and electrocatalytic activities of cobalt, iron and manganese phthalocyanine complexes axially co-ordinated to mercaptopyridine self-assembled monolayer at gold electrodes. Electrochim Acta 51:2669

    Article  CAS  Google Scholar 

  29. Lakshminarayanan V, Sur UK (2003) Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface. Pramana J Phys 61:361

    Article  CAS  Google Scholar 

  30. Pillay J, Ozoemena KI (2007) Efficient electron transport across nickel powder modified basal plane pyrolytic graphite electrode: Sensitive detection of sulfhydryl degradation products of the V-type nerve agents. Electrochem Comm 9:1816

    Article  CAS  Google Scholar 

  31. Sabatani E, Rubinstein I (1987) Organized self-assembling monolayers on electrodes. 2. Monolayer-based ultra-microelectrodes for the study of very rapid electrode kinetics. J Phys Chem 91:6663

    Article  CAS  Google Scholar 

  32. Pillay J, Ozoemena KI (2007) Single-walled carbon nanotube-induced crystallinity on the electropolymeric film of tetra-amino phthalocyaninato nickel (II) complex: Impact on the rate of heterogeneous electron transfer. Chem Phys Lett 441:72

    Article  CAS  Google Scholar 

  33. Khene S, Geraldo DA, Togo CA, Limson J, Nyokong T (2008) Synthesis, electrochemical characterization of tetra- and octa-substituted dodecyl-mercapto tin phthalocyanines in solution and as self-assembled monolayers. Electrochim Acta 54:183

    Article  CAS  Google Scholar 

  34. Yakuki S, Fujii S-I (2009) Hydrogen peroxide biosensor based on a polyion complex membrane containing peroxidase and toluidine blue, and its application to the fabrication of a glucose sensor. Microchim Acta 164:173

    Article  Google Scholar 

  35. Wang L, Wang E (2004) A novel hydrogen peroxide sensor based on horseradish peroxidase immobilized on colloidal Au modified ITO electrode. Electrochem Comm 6:225

    Article  CAS  Google Scholar 

  36. Ji X, Huang-Xian J, Hong-Yuan C (2000) Direct electrochemistry of horseradish peroxidase immobilized on a colloid/cysteamine-modified gold electrode. Anal Biochem 278:22

    Article  Google Scholar 

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Acknowledgements

This work was supported by Mintek through Project AuTEK and the Department of Science and Technology (DST)/Mintek Nanotechnology Innovation Centre (NIC) and by National Research Foundation (NRF) through DST/NRF South Africa Research Chairs Initiative for Professor of Medicinal Chemistry and Nanotechnology as well as Rhodes University.

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Authors and Affiliations

  1. Nanotechnology Innovation Centre, Advanced Materials Division, Mintek, Private Bag X3015, Randburg, 2125, South Africa

    Philani Mashazi

  2. Nanotechnology Innovation Centre—Sensors, Chemistry Department, Rhodes University, P.O. Box 94, Grahamstown, 6140, South Africa

    Philani Mashazi & Tebello Nyokong

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  1. Philani Mashazi
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  2. Tebello Nyokong
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Correspondence to Tebello Nyokong.

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Mashazi, P., Nyokong, T. Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes. Microchim Acta 171, 321–332 (2010). https://doi.org/10.1007/s00604-010-0438-6

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  • DOI: https://doi.org/10.1007/s00604-010-0438-6

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