Voltammetric Study and Rapid Quantification of Resorcinol in Hair Dye and Biological Samples Using Ultrasensitive Maghemite/MWCNT Modified Carbon Paste Electrode

Increased concern over the risk resorcinol (RS) pose to ecology and humans, led to its position in European Union Category 1 list of endocrine disruptors. Legal measures restricted RS utilization and hence crucial to monitor its levels in the environment. Herein we report development of highly efficient and economically viable electrochemical sensor for quantitative determination of RS based on 77Maghemite/MultiWall Carbon Nanotube (M/MWCNT) modified carbon paste electrode. M/MWCNT was synthesized via strategic IR irradiation for the first time, a promising approach to overcome other complicated chemical routes. Powder X‐ray diffraction (PXRD), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and Energy dispersive X‐ray (EDX) were used for characterization. Using Differential Pulse Voltammetry (DPV), we report the lowest detection limit at 0.02 μM. The potential application of the sensor was accomplished as a result of excellent recoveries made from real samples fortified with RS. Results indicated the proficiency of the sensor reliable for rapid, onsite monitoring of RS water contamination and in biological matrices.     

Effects of the dispersion methods in Pluronic F108 on the size and the surface composition of MWCNTs and their implications in toxicology assessment

Multi-walled carbon nanotubes (MWCNTs) were dispersed in water and in a Pluronic F108 solution by four different dispersion methods (stirring, bath sonication, stirring followed by bath sonication, and sonication probe). The effect of the dispersion methods were evaluated in terms of the particle size distribution, the agglomerates size, and the exfoliated fraction produced, as well as in terms of the surface and bulk chemical composition. Energy dispersive X-ray, X-ray photoelectron spectroscopy, and centrifugal liquid sedimentation techniques were used to characterize pristine MWCNTs and their dispersion. It is shown that, irrespective of the dispersion methods used, the MWCNTs are strongly wrapped with the biocompatible surfactant Pluronic F108, thereby modifying the external surface of the MWCNTs. Some shortening of MWCNTs and more wrapping are also observed when sonication methods are used. These observations raise questions as to the validity of results obtained in toxicology tests, in vitro and in vivo, were such methods of dispersion procedures are used.     

Anchoring of sulfur‐containing alkylphosphonic and semifluorinated alkylphosphonic molecules on a polycrystalline aluminum substrate

Self‐assembly on a polycrystalline aluminum substrate of two sulfur‐containing alkylphosphonic acids, CH₃? (CH₂)₁₁? S? (CH₂)₂? PO(OH)₂, and CF₃? (CF₂)₇? (CH₂)₂? S? (CH₂)₂? PO(OH)₂, has been compared with CH₃? (CH₂)₁₅? PO(OH)₂. The reaction of the phosphonic head groups with the hydroxyls at the alumina surface to form phosphonates was studied with X‐ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection‐absorption spectroscopy (PM‐IRRAS). Barrier effects of the resulting layers was assessed by electrochemical polarization curves. With the conditions used in the present work for the self‐assembly reaction, it appears that the sulfur‐containing molecules do not perform as well as CH₃? (CH₂)₁₅? PO(OH)₂ in terms of film quality. Questions are raised about the possibility that the sulfur‐containing molecules could undergo cleavage during surface modification. Copyright © 2008 John Wiley & Sons, Ltd.     

Aminealkylthiol and dithiol self-assembly as adhesion promoter between copper substrate and epoxy resin

To improve adhesion between copper and epoxy resin in printed circuit board, a roughness treatment of copper has been widely used. Nevertheless, new adhesion promoters have to be developed to face the miniaturization and sophistication of the electronic device. Self-assembled monolayers have met increasing interest in this field by using them as coupling agent between copper and the epoxy resin.This paper presents the deposition of an epoxy resin on copper modified by amine alkylthiol and dithiol monolayers and highlights the benefit brought by the monolayer in terms of adhesion.The chemical linkage between the amine SAMs and the epoxy function has been proved by the deposition on a short epoxy fragment, the 2-(4-fluorophenoxy-methyl)oxirane. The deposition of an epoxy resin mixed with amine curing agent has then been successfully achieved on amine terminated SAMs. The resulting polymer is homogeneous and well adherent on their surface, while the adhesion is lower on bare copper and not existing on methyl terminated SAMs. The formation of chemical bond Cu-S and N-epoxy is thus essential to increase the adhesion strength between copper and the polymer.     

Grafting of bifunctional phosphonic and carboxylic acids on Phynox: Impact of induction heating

Phynox, a cobalt-chromium alloy, exhibits interesting mechanical properties making it a valuable material for a number of applications. However, its applications (especially biomedical ones) often require specific surface properties that can be imparted via suitable surface functionalizations. Based on Faraday's law of induction, induction heating is a widely used method to heat metallic substrates directly and contactless. The aim of this work is to compare the influence of induction heating and a conventional heating method on the functionalization of Phynox surfaces with bifunctional (6-phosphonohexanoic and 11-phosphoundecanoic acids) monolayers in order to create a platform for a large variety of post-grafting chemical reactions, e.g. with alcohols and amines, to modify and control the surface properties. In a first part, we assess the influence of the heating method on the interaction between the two terminal moieties of the 6-phosphonohexanoic and 11-phosphoundecanoic acids and the Phynox surface by studying the grafting of n-dodecylphosphonic acid and n-dodecanoic acid separately. The suitability of such bifunctional molecules for post-grafting chemical reactions has then been assessed by studying the post-grafting of a fluorinated alcohol by the Steglich esterification reaction between the carboxylic end of the grafted bifunctional molecules and the alcohol function of the post-grafted molecule. It has been shown that induction heating can lead to a much more selective adsorption of bifunctional molecules on the surface of Phynox, leaving a higher amount of free carboxylic acid functions to react during the second modification step.     

Preparation of a polyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction

We report on the fabrication and performances of a solid-phase microextraction (SPME) fiber based on a stainless steel wire coated with a covalently attached polyacrylonitrile (PAN)/multi-walled carbon nanotubes (MWCNTs) composite. This new coating is obtained by atom transfer radical polymerization (ATRP) of acrylonitrile mixed with MWCNTs. ATRP is initiated from 11-(2-bromo-2-methylpropionyloxy)-undecyl-phosphonic acid molecules grafted on the wire surface via the phosphonic acid group. The extraction performances of the fibers are assessed on different classes of compounds (polar, non-polar, aromatic, etc.) from water solutions by headspace extraction. The optimization of the parameters affecting the extraction efficiency of the target compounds was studied as well as the reproducibility and the repeatability of the fiber. The fibers sustain more than 200 extractions during which they remain chemically stable and maintain good performances (detection limits lower than 2 μg/l, repeatability, etc.). Considering their robustness together with their easy and inexpensive fabrication, these fibers could constitute promising alternatives to existing products.     

High electrocatalytic oxidation of folic acid at carbon paste electrode bulk modified with iron nanoparticle-decorated multiwalled carbon nanotubes and its application in food and pharmaceutical analysis

Ionics - A simple and rapid method was employed for the modification of carbon paste electrode with iron nanoparticle-decorated multiwalled carbon nanotubes (MCPE/Fe-MWCNTs). The synergistic effect...     

1-Dodecanethiol self-assembled monolayers on cobalt

Cobalt and its alloys are used in a broad range of application fields. However, the use of this metal is especially limited by its strongly oxidizable nature. The use of alkanethiol self-assembled monolayers (SAMs) is a very efficient way to protect against such oxidation and/or to inhibit corrosion. This surface modification method has been particularly applied to oxidizable metals such as copper or nickel, yet the modification of cobalt surfaces by alkanethiol SAMs received limited attention up to now. In this work, we study the influence of parameters by which to control the self-assembly process of 1-dodecanethiol monolayers on cobalt: nature of the surface pretreatment, solvent, immersion time, and concentration. Each of these parameters has been optimized to obtain a densely packed and stable monolayer able to efficiently prevent the reoxidation of the modified cobalt substrates. The obtained monolayers were characterized by X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy, and contact angle measurements. The stability of the optimized 1-dodecanethiol monolayer upon air exposure for 28 days has been confirmed by XPS.     

Electrochemical and spectroscopic study of the self-assembling mechanism of normal and chelating alkanethiols on copper

The self-assembly of aliphatic thiol (RSH), dithiol (R(SH)(2)), and dithiocarboxylic acid (RS(2)H) onto mildly oxidized and highly oxidized copper was studied in real time by in situ electrochemical impedance spectroscopy (EIS). Ex situ characterization of the films was carried out using linear sweep voltammetry (LSV), polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). In situ EIS studies found a very fast adsorption of RSH, R(SH)(2), and RS(2)H (within 10-15 s). This fast adsorption step is followed by the long-term additional adsorption and consolidation of SAM. However, the self-assembly of RS(2)H passes through an intermediate step of molecule rearrangement for around 10 to 30 min after around 2 to 7 min of self-assembly. The binding of both sulfur moieties of R(SH)(2) with Cu happens simultaneous. The oxide reduction capacity of RSH, R(SH)(2), and RS(2)H was good. However, the XPS studies showed the decomposition of RS(2)H-based SAMs to Cu(2)S. Monolayers prepared on both mildly oxidized and heavily oxidized Cu with R(SH)(2) had the highest stability. Monolayers of RS(2)H showed the least stability on both mildly oxidized and heavily oxidized Cu. Although RSH-based SAMs had good organization on both mildly oxidized and highly oxidized Cu, R(SH)(2)-based SAMs did not show good organization in either case. The RS(2)H monolayer had good organization only on mildly oxidized Cu.     

Comparison between CH3(CH2)15SH and CF3(CF2)3(CH2)11SH monolayers on electrodeposited silver

In this paper, two monolayers self-assembled on a silver substrate are compared: a monolayer of n-hexadecanethiol and a monolayer of n-11-perfluorobutylundecanethiol. The protecting properties of both monolayers have been extensively studied by X-ray photoelectron spectroscopy, contact angle, polarization modulation infrared reflection absorption spectroscopy, conventional electrochemical techniques (polarization curves and electrochemical impedance spectroscopy), and scanning vibrating electrode technique. Both monolayers were successfully self-assembled but organization is slightly different, the fluorinated segment introduces small disorganization. Nevertheless, good homogeneous corrosion protection is observed for each monolayer.