Erwann Luais

The Fabrication of Stable Gold Nanoparticle-Modified Interfaces for Electrochemistry

Forming stable gold nanoparticle (AuNP)-modified surface is important for a number of applications including sensing and electrocatalysis. Herein, tethering AuNPs to glassy carbon (GC) surfaces using surface bound diazonium salts is investigated as a strategy to produce stable AuNP surfaces. GC electrodes are first modified with 4-aminophenyl (GC-Ph-NH(2)), and then the terminal amine groups are converted to diazonium groups by incubating the GC-Ph-NH(2) interface in NaNO(2) and HCl solution to form a 4-phenyl diazonium chloride-modified interface (GC-Ph-N(2)(+)Cl(-)). Subsequently AuNPs are immobilized on the interface by electrochemical reduction to give a 4-phenyl AuNP-modified interface (GC-Ph-AuNP). For comparison, 4-aminophenyl AuNP- and 4-thiophenol AuNP-modified GC interfaces (GC-Ph-S-AuNP and GC-Ph-NH-AuNP), in which AuNPs are tethered to the surfaces by forming S-Au and NH-Au bond, respectively, were also prepared. Cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy are used to characterize these fabricated interfaces. The AuNP on GC-Ph-AuNP surfaces demonstrate good stability under sonication in Milli-Q water, during electrochemical treatment in 0.05 M H(2)SO(4) solution, and over several weeks. By contrast, the GC-Ph-NH-AuNP and GC-Ph-S-AuNP surfaces showed significant particle losses under equivalent conditions.

Distance-dependent electron transfer at passivated electrodes decorated by gold nanoparticles

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.

Zwitterionic Phenyl Layers: Finally, Stable, Anti-Biofouling Coatings that Do Not Passivate Electrodes

Organic coatings on electrodes that limit biofouling by proteins but are of sufficiently low impedance to still allow Faradaic electrochemistry to proceed at the underlying electrode are described for the first time. These organic coatings formed using simple aryl diazonium salts present a zwitterionic surface and exhibit good electrochemical stability. The layers represent a low impedance alternative to the oligo (ethylene glycol) (OEG)-based anti-biofouling coatings and are expected to find applications in electrochemical biosensors and implantable electrodes. Two different zwitterionic layers grafted to glassy carbon surfaces are presented and compared to a number of better-known surfaces, including OEG-based phenyl-layer-grafted glassy carbon surfaces and OEG alkanethiol SAMs coated on gold, to allow the performance of these new layers to be compared to the body of work on other anti-biofouling surfaces. The results suggest that phenyl-based zwitterionic coatings are as effective as the OEG SAMs at resisting the nonspecific adsorption of bovine serum albumin and cytochrome c, as representative anionic and cationic proteins at physiological pH, whereas the impedance of the zwitterionic phenyl layers are two orders of magnitude lower than OEG SAMs.

Studies on the Effect of Solvents on Self-Assembled Monolayers Formed from Organophosphonic Acids on Indium Tin Oxide

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.

Grafting of poly(ethylene glycol) on click chemistry modified Si(100) surfaces.

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.

The influence of organic-film morphology on the efficient electron transfer at passivated polymer-modified electrodes to which nanoparticles are attached

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.

Depth-resolved chemical modification of porous silicon by wavelength-tuned irradiation

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.

The rapid formation of functional monolayers on silicon under mild conditions

We report on an exceedingly mild chemical functionalization of hydrogen-terminated Si(100) with unactivated and unprotected bifunctional α,ω-dialkynes. Monolayer formation occurs rapidly in the dark, and at room temperature, from dilute solutions of an aromatic-conjugated acetylene. The method addresses the poor reactivity of p-type substrates under mild conditions. We suggest the importance of several factors, including an optimal orientation for electron transfer between the adsorbate and the Si surface, conjugation of the acetylenic function with a π-system, as well as the choice of a solvent system that favors electron transfer and screens Coulombic interactions between surface holes and electrons. The passivated Si(100) electrode is amenable to further functionalization and shown to be a viable model system for redox studies at non-oxide semiconductor electrodes in aqueous solutions.

Surface Epitope Coverage Affects Binding Characteristics of Bisphenol-A Functionalized Nanoparticles in a Competitive Inhibition Assay

The biomolecule interface is a key element in immunosensor fabrication, which can greatly influence the sensor performance. This paper explores the effects of surface epitope coverage of small molecule functionalized nanoparticle on the apparent affinity (avidity) of antibody in a competitive inhibition assay using bisphenol-A (BPA) as a model target. An unconventional two-antibody competitive inhibition ELISA (ci-ELISA) using thiolated BPA modified gold nanoparticles (cysBPAv-AuNP) as a competing reagent was devised for this study. It was shown that the antibody complexation with cysBPAv-AuNPs required a minimum number of surface epitopes on the nanoparticle to form a sufficiently strong interaction and reliable detection. The binding of cysBPAv-AuNP to anti-BPA antibodies, for limited antibody binding sites, was enhanced by a greater number of epitope-modified nanoparticles (cysBPAv-AuNP) as well as with higher epitope coverage. Increasing the molar concentration of epitope present in an assay enhanced the binding between anti-BPA antibodies and cysBPAv-AuNP. This implies that, to increase the limit of detection of a competitive inhibition assay, a reduced molar concentration of epitope should be applied. This could be achieved by either lowering the epitope coverage on each cysBPAv-AuNP or the assay molar concentration of cysBPAv-AuNP or both of these factors.

Demonstrating the Use of Bisphenol A-functionalised Gold Nanoparticles in Immunoassays

Spherical gold nanoparticles (5-nm diameter) were modified with a small-molecule thiolated bisphenol A (BPA) ligand to achieve an estimated coverage of ~3.3 × 10–10 mol cm–2, or 180 ligands per particle. The modified particles were tested in an enzyme-linked immunosorbent assay (ELISA) format to measure functionality and were shown to bind specifically to anti-BPA antibody while resisting the non-specific adsorption of an antibody with no affinity for BPA. It was found that the use of 10 % ethanol as a co-solvent was required in the ELISA as aqueous buffers alone resulted in poor binding between anti-BPA antibody and the functionalised nanoparticles. This is likely due to the hydrophobic nature of the BPA ligand limiting its solubility, and therefore its availability for antibody interactions, in purely aqueous environments. To our knowledge, this is the first example of a nanoparticle modified with a small organic molecule being used in an ELISA assay.