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    Bifunctional Polyoxometalates for Planar Gold Surface Nanostructuration and Protein Immobilization

    Year: 2012

    Journal: J. Phys. Chem. C, 2012, 116 (24), pp 13217–13224, 20120922

    Authors: Dimitri Mercier †, Souhir Boujday *‡§, Cyrine Annabi ‡§, Richard Villanneau †, Claire-Marie Pradier ‡§, and Anna Proust *†

    Last authors: Anna Proust

    Organizations: † Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, UPMC Univ Paris 06, Université Pierre et Marie Curie, 4 place Jussieu, Case 42, 75252, Paris Cedex 05, France ‡ UPMC Univ Paris 06, UMR CNRS 7197, Laboratoire de Réactivité de Surface, F75005 Paris, France § CNRS, UMR 7197, Laboratoire de Réactivité de Surface, F75005 Paris, France Institut Universitaire de France, 103 Bd Saint-Michel, 75005 Paris, France

    Country: France

    Surface nanostructuration was successfully achieved by binding the polyoxometalate (POM) (NBu4)3[PW11O39{(SiC6H4NH2)2O}] covalently onto planar gold surfaces. To do so, POMs functionalized with two terminal amino groups were synthesized and reacted with a mercaptoundecanoic acid self-assembled monolayer adsorbed on gold. These amine-terminated POM macroanions proved to be remarkably efficient as nanostructuring agents. Using polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS), photoelectron spectroscopy (XPS), and atomic force microscopy (AFM), conditions were optimized to elaborate a dense and well-dispersed layer of POMs, leaving a “free” amine function for the further linkage of proteins. Antirabbit immunoglobulins (anti-rIgGs) were thus grafted on the POM-structured layer, and the recognition of their specific target, rabbit immunoglobulin (rIgGs), was tested by using a quartz crystal microbalance with dissipation measurement (QCM-D). The recognition was good and highly specific, indicating that an efficient, nanostructured biosensor has been constructed. The method reported herein can be easily applied, not requiring any sophisticated experimental setup, and is promising for the patterning of any molecular probes bearing amine groups.