Application of ZP chemistry for the immobilization of polycyclic aromatic hydrocarbons and enzymes on gold, boron doped diamond, indium tin oxide and quartz.

Paweł G. Krysiński 1Maciej Mazur 1Gary J. Blanchard 2

1. Warsaw University, Faculty of Chemistry, Pasteura 1, Warszawa 02-093, Poland
2. Michigan State University (MSU), East Lansing, MI 48824-1322, United States


Controlling the molecular structure and organization of interfacial region between solid substrate and electrolyte solution has become a routine in various domains of chemistry [1,2]. In this paper we show the formation of monomolecular layer of pyrene, derivatized with alkyl carboxylic acid side chains of various lengths and terminal functionalities, on the surface of gold, boron-doped diamond (BDD), indium-tin oxide (ITO) and quartz by means of zirconium phosphonate (ZP) chemistry. The choice of pyrene ring systems was based upon their use as optical probes of polarity and viscosity of local environment. Moreover, these molecules are electroactive and this enabled us to evaluate the surface coverage with these molecules. The ability to covalently bind such probes to variety of surfaces, including boron-doped diamond, due to its excellent electro-optical and chemical properties, will broaden the field of relaxation dynamics studies of these molecules. We have used steady-state fluorescence emission spectroscopy and electrochemical techniques to study the behavior of monomolecular films formed on different surfaces. We show that surface modification is possible on both hydrated oxide surfaces (ITO and quartz) as well as on oxidized carbon substrates (BDD). The latter case is especially interesting since BDD is widely believed to be inert and thus difficult to modify. Such modified substrates were subsequently used to immobilize laccase, preserving catalytic activity of this enzyme.

Acknowledgement: The authors are grateful to Professor Greg Swain, Chemistry Dept., Michigan State University, USA, for his generous gift of BDD thin films. This work was supported by the Ministry of Scientific Research and Information Technology in 2004-2007, Project No. PBZ 18-KBN098/T09/2003. The NSF-PAS mobility grant (PK) is also acknowledged.

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Presentation: Keynote lecture at SMCBS'2005 Workshop, by Paweł G. Krysiński
See On-line Journal of SMCBS'2005 Workshop

Submitted: 2005-07-05 14:34
Revised:   2009-06-07 00:44
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