The electrochemical formation and characterization of decanoic, myristic, palmitic, and stearic acid self-assembled monolayers on a native oxide surface of 316L stainless steel have been studied. This work describes a new approach to surface modification of stainless steel in which the self-assembly of n-alkanoic acids is facilitated by applying a potential to the stainless steel in an organic electrolyte solution. While decanoic acid forms a disorganized monolayer as a result of sweeping the potential in an acetonitrile solution containing 0.1 mM of the respective acid, longer acids, that is, myristic and palmitic acids, form highly ordered closed-packed monolayers. This electrochemical approach results in highly reproducible monolayers that are deposited within a shorter time than the traditional assembly process. The monolayers were characterized by cyclic voltammetry, double-layer capacity (ac voltammetry), contact angle measurements, X-ray photoelectron spectroscopy, and external reflection-absorption Fourier transform infrared spectroscopy. The utilization and implications of this modification technique are discussed.
Electropolymerization of medical devices such as cardiovascular stents may posses advantages including a simple and reproducible process with the ability to control the thickness, adherence, and composition of the coating by the duration and intensity of the applied current, the monomer composition and concentration, the solvent, and the reaction conditions. The properties of the polymer can also be controlled by copolymerization of different monomers, grafting substituents to a functionalized polymer, and by entrapping biomolecules. This article describes the synthesis of a range of pyrrole-based monomers and their electrocoating onto stainless steel surfaces. N-substituted pyrrole monomers with C1-C18 alkyl chains and poly (ethylene glycol) chains were synthesized in good yields and purity. Electropolymerization of these monomers provided uniform coatings with different hydrophobicities. Studies now focus on the incorporation of drugs in the coated device for release from the surface.
The applicability of thin sol-gel films as selective interfaces in electrochemical sensors has been examined. This requires not only to create a selective interface but also to enable facile diffusion of the analytes across the films. Creation of selectivity has been aimed by molecularly imprinting an electroactive species in the course of sol-gel formation. We have focused primarily on imprinting an iron(II) complex, i.e., tris(2,2'-bipyridine)iron(II) (Fe(bpy) 2 3 , as a means of selectively determining iron(II) in aqueous solution. Hence, the effect of different parameters, such as the composition of the sol-gel film and the hydrolysis and drying time, on the diffusion of Fe(bpy) 2 3 , has been studied. We find that diffusion can be remarkably enhanced upon adding polyethylene glycol or a surfactant, such as decanoic acid. Nevertheless, so far we have not been able to develop thin films, which exhibit selectivity towards this inorganic species. The difficulties in designing such selective interfaces for heavy metals as opposed to organic species is demonstrated by successfully applying the same approach for designing a selective interface for diethyl-p-nitrophenyl phosphate (paraoxon).
The formation of a self-assembled monolayer significantly promotes the adhesion of electrodeposited polypyrrole on stainless steel. The monolayer affects the nucleation and growth mechanism of polypyrrole as a result of its hydrophobic nature. This was confirmed by analyzing current-time transients of the initial stages of electropolymerization and was in agreement with AFM images.
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