Sabrina Sam

Molecular monolayers on silicon as substrates for biosensors

(111) silicon surfaces can be controlled down to atomic level and offer a remarkable starting point for elaborating nanostructures. Hydrogenated surfaces are obtained by oxide dissolution in hydrofluoric acid or ammonium fluoride solution. Organic species are grafted onto the hydrogenated surface by a hydrosilylation reaction, providing a robust covalent Si-C bonding. Finally, probe molecules can be anchored to the organic end group, paving the way to the elaboration of sensors. Fluorescence detection is hampered by the high refractive index of silicon. However, improved sensitivity is obtained by replacing the bulk silicon substrate by a thin layer of amorphous silicon deposited on a reflector. The development of a novel hybrid SPR interface by the deposition of an amorphous silicon-carbon alloy is also presented. Such an interface allows the subsequent linking of stable organic monolayers through Si-C bonds for a plasmonic detection. On the other hand, the semiconducting properties of silicon can be used to implement field-effect label-free detection. However, the electrostatic interaction between adsorbed species may lead to a spreading of the adsorption isotherms, which should not be overlooked in practical operating conditions of the sensor. Atomically flat silicon surfaces may allow for measuring recognition interactions with local-probe microscopy.

Active Acetylcholinesterase Immobilization on a Functionalized Silicon Surface

In this work, we studied the attachment of active acetylcholinesterase (AChE) enzyme on a silicon substrate as a potential biomarker for the detection of organophosphorous (OP) pesticides. A multistep functionalization strategy was developed on a crystalline silicon surface: a carboxylic acid-terminated monolayer was grafted onto a hydrogen-terminated silicon surface by photochemical hydrosilylation, and then AChE was covalently attached through amide bonds using an activation EDC/NHS process. Each step of the modification was quantitatively characterized by ex-situ Fourier transform infrared spectroscopy in attenuated-total-reflection geometry (ATR-FTIR) and atomic force microscopy (AFM). The kinetics of enzyme immobilization was investigated using in situ real-time infrared spectroscopy. The enzymatic activity of immobilized acetylcholinesterase enzymes was determined with a colorimetric test. The surface concentration of active AChE was estimated to be Γ = 1.72 × 10(10) cm(-2).

Localized surface plasmon resonance interfaces coated with poly[3-(pyrrolyl)carboxylic acid] for histidine-tagged peptide sensing.

The paper reports on a novel localized surface plasmon resonance (LSPR) substrate architecture for the immobilization and detection of histidine-tagged peptides. The LSPR interface consists of an ITO (indium tin oxide) substrate coated with gold nanostructures. The latter are obtained by thermal deposition of a thin (2 nm thick) gold film followed by post-annealing at 500 °C. The LSPR interface was coated with poly[3-(pyrrolyl)carboxylic acid] thin films using electrochemical means. The ability of the LSPR interfaces coated with poly[3-(pyrrolyl)carboxylic acid] to chelate copper ions was investigated. Once loaded with metal ions, the modified LSPR interface was able to bind specifically to histidine-tagged peptides. The binding process was followed using LSPR.

Electrochemical Sensor for Detection of Para-Nitrophenol Based on Modified Porous Silicon

The behavior of a modified porous silicon surface (PSi) with polythiophene (PTh) for para-nitrophenol (p-NPh) detection by cyclic voltammetry was studied. Nitrophenols are organic compounds which are the most used in the production of pesticides but also in the dyes and pharmaceuticals. In particular, p-NPh is a toxic derivative of the parathion insecticide and is considered as major toxic polluant because it is soluble and stable in water so it can affect soil. Porous silicon was prepared by electrochemical etching and it was modified by an oxide layer. PTh films were grown on this surface using electropolymerization in acetonitrile in the presence of thiophene monomer.The morphology of the fabricated PSi/PTh hybrid structures were characterized by scanning electron microscopy (SEM). Cyclic voltammetry and amperometry were used to study the proposed electrochemical p-NPh sensor. The performance of the proposed sensor was tested under differents conditions and we note a very high sensitivity; in particular, the linearity of the sensor for the detection of para-nitrophenol was observed from 3×108 to 1.5 ×104M with a detection limit of 6×109M.

Voltammetric Behavior of Peptide-Modified Porous Silicon after Metal Complexation

Hybrid nanomaterials based on organic layer covalently grafted on porous silicon (PSi) nanostructure appear as promising systems for innovative applications such as detecting of traces amounts and/or removing metal cations in water effluents. In this work, we focused on the functionalization of the PSi nanostructure by the peptide GlyCysGlyCys, which forms stable complexes with metal ions. This property is exploited to achieve toxic metal recognition in water using electrochemical methods. Peptide immobilization was achieved using multi-step reactions; GlyCysGlyCys was anchored on a previously prepared carboxyl-terminated PSi surface, using EDC/NHS coupling agents. This scheme is compatible with the mild conditions required for preserving the probe activity of the peptide. At each step of the functionalization, the surface was monitored by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Electrochemical behavior of such modified electrode was carried out after Nickel accumulation on the surface, by means of cyclic voltammetry. The recorded cyclic voltammograms showed a quasi-irreversible process corresponding to the Ni2+/Ni0 couple.