ABSTRACT
For the first time, we have investigated the beneficial effects of non-cavitating coupling fluids and their moderate overpressures in enhancing mass-transfer and acoustic energy transfer in a double cell micro-sonoreactor. Silicon and engine oils of different viscosities were used as non-cavitating coupling fluids. A formulated monoethylene glycol (FMG), which is a regular cooling fluid, was also used as reference. It was found that silicon oil yielded a maximum acoustic energy transfer (3.05 W/cm2) from the double jacketed cell to the inner cell volume, at 1 bar of coupling fluid overpressure which was 2.5 times higher than the regular FMG cooling fluid. It was also found that the low viscosity engine oil had a higher acoustic energy value than that of the high viscosity engine oil. In addition, linear sweep voltammograms (LSV) were recorded for the quasi-reversible Fe2+/Fe3+ redox couple (equimolar, 5 × 10-3 M) on a Pt electrode in order to determine the mass-transport limited current density (jlim) and the dimensionless Sherwood number (Sh). From the LSV data, a statistical analysis was performed in order to determine the contribution of acoustic cavitation in the current density variation |Δj|average. It was found that silicon oil at 1 bar exhibited a maximum current density variation, |Δj|average of ~2 mA/cm2 whereas in the absence of overpressure, the high viscosity engine oil led to a maximum |Δj|average which decreased gradually with increasing coupling fluid overpressure. High viscosity engine oil gave a maximum Sh number even without any overpressure which decreased gradually with increasing overpressure. The Sh number for silicon oil increased with increasing overpressure and reached a maximum at 1 bar of overpressure. For any sonoelectrochemical processes, if the aim is to achieve high mass-transfer and acoustic energy transfer, then silicon oil at 1 bar of overpressure is a suitable candidate to be used as a coupling fluid.
ABSTRACT
Self-assembling of undecanthiol (C11SH) on polycrystalline gold was investigated under two different conditions. The kinetics of C11SH grafting was studied without and under high frequency ultrasound irradiation. Two electrochemical experiments were extensively carried out in order to determine electrochemical surface blocking of adsorbed layers as a function of grafting time: chronoamperometry in-situ monitoring and cyclic voltammetry. Interestingly, the grafting process is highly accelerated under sonication, and C11SH modified substrates of good quality are obtained after 3h' immersion under ultrasound irradiation. This would allow elaboration of high-quality alkanethiol modified samples within much shorter times. Water contact angle measurements and X-ray Photoelectron Spectroscopy (XPS) confirmed the presence of adsorbed undecanthiol on the gold surface. A very close link between electrochemical blocking, surface hydrophobicity and species chemical grafting was established.
ABSTRACT
Self-assembly of alkylphosphonic acids on stainless steel was investigated under different conditions. Four different alkylphosphonic acids exhibiting alkyl chain of various size were synthesized and studied: butylphosphonic acid (C4P), octylphosphonic acid (C8P), decylphosphonic acid (C10P), and hexadecylphosphonic acid (C16P). Electrochemistry experiments were extensively carried out in order to determine electrochemical surface blocking of adsorbed layers in function of grafting time. In term of surface blocking, an 8h modification time was optimal for all alkylphosphonic acids. Longer immersion times lead to degradation of adsorbed layers. For the first time, grafting of C16P was studied under high frequency ultrasound irradiation. Interestingly, grafting process is highly accelerated under sonication and well-covering C16P modified substrates are obtained after 1h of immersion under ultrasound irradiation. This would allow to elaborate high-quality alkylphosphonic acids modified samples within much shorter times. Water contact angles measurements and X-ray Photoelectrons Spectroscopy (XPS) confirmed presence of adsorbed alkylphosphonic acids on stainless steel surface. A very tight link between electrochemical blocking, surface hydrophobicity and species chemical grafting was established.
ABSTRACT
Electron transfer inside proteins plays a central role in their reactivity and biological functions. Herein, we developed a combined approach by gamma radiolysis and electrochemistry which allowed a deep insight into the reactivity of Human centrin 2, a protein very sensitive to oxidative stress and involved in several key biological processes. This protein bears a single terminal tyrosine and was observed to be extremely sensitive to ionizing radiation sources, leading to a tyrosine dimer. By cyclic voltammetry in the 100-1000 V s(-1) range, its redox potential and dimerization rate could be evaluated. Accordingly, reaction in solution with a redox mediator revealed an efficient catalysis. Finally, protein denaturation by a progressive increase in temperature was proportional to a decrease of dimerization radiolytic yield. Our results thus demonstrated that the protein structure plays a major role in oxidation sensitivity. This leads to meaningful results to understand protein redox reactivity.
Subject(s)
Calcium-Binding Proteins/chemistry , Cell Cycle Proteins/chemistry , Tyrosine/chemistry , Catalysis , Electrochemical Techniques , Electron Transport , Gamma Rays , Humans , Models, Molecular , Oxidation-Reduction , Protein Conformation/radiation effectsABSTRACT
A variety of coatings based on electrosynthesized polypyrrole were deposited on zinc coated steel in presence or absence of ultrasound, and studied in terms of corrosion protection. Cr III and Cr VI commercial passivation were used as references. Depth profiling showed a homogeneous deposit for Cr III, while SEM imaging revealed good surface homogeneity for Cr VI layers. These chromium-based passivations ensured good protection against corrosion. Polypyrrole (PPy) was also electrochemically deposited on zinc coated steel with and without high frequency ultrasound irradiation in aqueous sodium tartrate-molybdate solution. Such PPy coatings act as a physical barrier against corrosive species. PPy electrosynthesized in silent conditions exhibits similar properties to Cr VI passivation with respect to corrosion protection. Ultrasound leads to more compact and more homogeneous surface structures for PPy, as well as to more homogeneous distribution of doping molybdate anions within the film. Far better corrosion protection is exhibited for such sonicated films.
