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Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Abstract

Modification of electrodes with nanometer-scale organically modified silica films with pore diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano cross-links or gold nanoparticles protected by dirhodium-substituted phosphomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. Ten-nanometer pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. Fifty-nanometer pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)6 3− and Ru(NH3)6 3+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

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Acknowledgments

This work was supported by the U.S. National Institutes of Health by grant R15GM087662-01 to JAC. Support for PJK and IAR was from the Foundation for Polish Science under Mistrz Program and by National Science Center (Poland) under Maestro Project 2012/04/AST400287.

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Correspondence to James A. Cox.

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Mehdi, B.L., Rutkowska, I.A., Kulesza, P.J. et al. Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids. J Solid State Electrochem 17, 1581–1590 (2013). https://doi.org/10.1007/s10008-013-2077-4

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  • DOI: https://doi.org/10.1007/s10008-013-2077-4

Keywords

  • Electrocatalysis
  • Phospholipids
  • Mesoporous ormosils
  • Macroporous ormosils
  • Layer-by-layer assembly
  • Ruthenium oxide
  • Dirhodium polyoxometalate