Search

The phenomenon of nanoparticles attached to an electrode passivated by an organic layer allowing efficient electron transfer between redox species in solution and the underlying electrode to be restored has resulted in Chazalviel and Allongue proposing a theory [Chazalviel, J.-N.; Allongue, P. J. Am. Chem. Soc.2011, 133, 762-764] to explain this phenomenon. The theory suggests that with electrode-organic layer-nanoparticle constructs, high exchange current densities, compared with when the nanoparticles are absent, results in the rate of electron transfer being independent of the thickness of the organic layer until a threshold thickness is exceeded. Thereafter, the thicker the organic layer, the slower the rate of electron transfer. Herein we provide the first experimental data to support this theory using a single experimental system that can show the transition from thickness independent electron transfer kinetics to distant dependent kinetics. This was achieved using ethylenediamine electrodeposited on a glassy carbon electrode. Different numbers of deposition cycles were applied in order to fabricate different thicknesses of the organic film. The deposited films showed progressively greater blocking abilities toward ruthenium hexamine, as a redox active probe in solution, as the films got thicker. Electron transfer kinetics of nanoparticle-decorated surfaces showed a change from thickness independent to thickness dependent as the organic layer exceeded an average thickness of 20 Å. Electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, ellipsometry, and atomic force microscopy were used to characterize the fabricated surfaces. 2012 American Chemical Society.

The impact of polymer-film morphology on the electron-transfer process at electrode/organic insulator/nanomaterial architectures is studied. The experimental data are discussed in the context of the most recent theory modelling the nanoparticle-mediated electron-transfer process at electrode/insulator/nanomaterial architectures proposed by Chazalviel and Allongue [J. Am. Chem. Soc. 2011, 133, 762-764]. A previous report [Anal. Chem. 2013, 85, 1073-1080] by us qualitatively verified the theory and demonstrates a transition from thickness-independent to thickness-dependent electron transfer as the layer thickness exceeds a certain threshold. This follow-up study explores a different polymer, poly(phenylenediamine), and focuses on the effect of the uniformity of organic film on electron transfer at these hybrid structures. Electron-transfer kinetics of modified surfaces, which were assessed using the redox species Ru(NH3)6 3+ in aqueous solution, showed that a thickness-dependent electron-transfer regime is achieved with poly(phenylenediamine). This is attributed to the sufficiently thin films never being fabricated with this polymer. Rather, it is suggested that thin poly(phenylenediamine) layers have a globular structure with poor film homogeneity and pinhole defects. Copyright 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent. 2013 American Chemical Society.

The ability to impart discrete surface chemistry to the inside and outside of mesoporous silicon is of great importance for a range of biomedical applications, from selective (bio)sensing to tissue-specific drug delivery. Here we present a generic strategy toward achieving depth-resolved functionalization of the external and internal porous surfaces by a simple change in the wavelength of the light being used to promote surface chemical reactions. UV-assisted hydrosilylation, limited by the penetration depth of UV light, is used to decorate the outside of the mesoporous structure with carboxylic acid molecules, and white light illumination triggers the attachment of dialkyne molecules to the inner porous matrix. 2012 American Chemical Society.

The preparation of self-assembled monolayers (SAMs) of organophosphonic acids on indium tin oxide (ITO) surfaces from different solvents (triethylamine, ethyl ether, tetrahydofuran (THF), pyridine, acetone, methanol, acetonitrile, dimethyl sulfoxide (DMSO), or water) has been performed with some significant differences observed. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and contact angle measurement demonstrated that the quality of SAMs depends critically on the choice of solvents. Higher density, more stable monolayers were formed from solvents with low dielectric constants and weak interactions with the ITO. It was concluded low dielectric solvents that were inert to the ITO gave monolayers that were more stable with a higher density of surface bound molecules because higher dielectric constant solvents and solvents that coordinate with the surface disrupted SAM formation. 2012 American Chemical Society.

A novel method to prepare redox monolayers on silicon electrodes has been developed that employs CuI-catalyzed oxidative acetylenic coupling reactions for molecular electronic type applications. As the first case study, ethynylferrocene was covalently immobilized onto an acetylene-terminated monolayer on a Si(100) surface to give a 1,3-diyne (CC-CC-) linked redox assembly. The derivatization process requires no protection/de-protection steps, nor activation procedures. The effect of the conjugated diyne linkage on the rate of electron transfer between tethered ferrocenyl units and the silicon electrode is benchmarked against well-established "click" products (i.e. 1,2,3-triazole linkage). The surfaces, after each step, are characterized thoroughly using X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The coupling chemistry provides a useful strategy for functionalizing silicon surfaces and contributes to an expanding repertoire of wet chemistry routes for the functionalization of solid substrates. This journal is the Owner Societies.