Study of (3-mercaptopropyl)trimethoxysilane reactivity on zinc: Comparison with organothiol and organosilane thin films

To assess the reactivity of both terminal functions of the (3-mercaptopropyl)trimethoxysilane molecule, three types of zinc substrate (mechanically polished, electrochemically reduced and electrochemically oxidized) were modified concurrently by 1H,1H,2H,2H-perfluorooctyl-triethoxysilane and 1H,1H,2H,2H-perfluorooctanethiol. Surface characterization has been carried out with X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy and contact angle measurements. Classical electrochemical techniques were employed to investigate corrosion inhibition of zinc along with thin films grafting. It is found that electrochemical oxidation enhances the grafting of the -Si(OCH₃)₃ groups while electrochemical reduction facilitates the formation of thiolate bonds, leading both to modified surfaces of much better quality compared to modified polished zinc samples.     

Electrochemical and spectroscopic study of C12H25X molecules adsorption on copper sheets, X (-SH, -S-S-, -SeH and -Se-Se-)

In this contribution, we explored the possibility of using selenol and selenide molecules to form self-assembled monolayers (SAMs) on copper, in order to check the influence of anchoring groups on SAMs quality and compared it to well-known thiolate assemblies (formed with thiol and disulfide molecules). Precisely, monolayers of pure alkane chains have been self-assembled on electroreduced bulk copper. The different selected molecules present the following reactive anchoring groups: thiol (R-SH), disulfide (R-S-S-R), selenol (R-SeH) and diselenide (R-Se-Se-R), where R = C₁₂H₂₅-. Electrochemical (cyclic voltammetry and scanning electrochemical microscopy) techniques and spectroscopic (X-ray photoelectron and polarization modulation infrared reflection absorption spectroscopy) have been used to characterize the surface composition and monolayer organization. Atomic force microscopy (AFM) measurements complete this study. All molecules analyzed have been shown to form monolayers of variable quality. The R-SH and R-SeH monolayers seem to lead to better organized and insulating layers than the R-S-S-R and R-Se-Se-R monolayers. However, the case of the diselenide is more complex and could lead to some interesting properties.     

7-Octenyltrimethoxysilane,a model coupling molecule to study the adhesion promotion of a silicone elastomer on an Al 2024 alloy

Ultra-thin layers of 7-octenyltrimethoxysilane (7-OTMS) and of 7-OTMS mixed with n-octyltrimethoxysilane (n-OTMS) (1/1 and 1/10 v/v) have been prepared as adhesion primers for silicone coatings on mechanically polished AA2024 aluminum alloy. The characterization of the silane grafting has been carried out by X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) and water contact angle measurements. Sylgard^®184 silicone has been spin-coated and cured on bare and modified aluminum to form 15 μm polymer films. Qualitative peel tests (ASTM D3359) and scanning electron microscopy (SEM) point to the beneficial effect of the 7-OTMS layer to the adhesion whereas mixed layers show comparatively poor adhesion.     

Multifunctional hybrid coating on titanium towards hydroxyapatite growth: Electrodeposition of tantalum and its molecular functionalization with organophosphonic acids films

Titanium and its alloys are base materials used in the dental and orthopaedic fields owing to suitable intrinsic properties: good biocompatibility, high corrosion resistance and excellent mechanical properties. However, the bonding between titanium and bone tissue is not always strong enough and can become a critical problem. In this context, the two main objectives of this paper are the increase of the corrosion resistance and the improvement of the hydroxyapatite (HAp) growth. The surface modification considered here is achieved in three main steps and consists in the elaboration of different inorganic and organic coatings. The first step is the elaboration of electrodeposition of tantalum on the titanium oxide film of a titanium substrate. The second step is the modification of the tantalum oxide coating with organophosphonic acids. The last step is the nucleation and growth of HAP on the outermost layer of the system by immersion in a simulated body fluid. The hybrid coating tantalum oxide/organophosphonic acids/molecular layer is shown to be promising for orthopaedic implants.     

Stability of self-assembled monolayers of organothiol mono and bipode on copper in presence of another organothiol solution

The stability of alkanethiol self-assembled monolayers (SAMs) on metallic substrates is an important aspect for further application. Some studies point out the poor stability of this coating and the displacement of alkanethiol from the monolayer by immersion in another alkanethiol solution.The aim of this work consists in a comparative investigation of self-exchange of three organothiols: 11-perfluorobutyl-1-thiol-undecane (or R_fSH), 2-dodecylpropane-1,3-dithiol (or R(SH)₂) and n-decanedithiocarboxylic (or RS₂H).The immersion of RS₂H monolayer into R_fSH solution (first approach) leads to the incorporation of thiol molecules into the defects of the initial SAMs followed by the displacement of RS₂H molecules by R_fSH. While for R_fSH SAM in presence of R(SH)₂ solution (second approach), longer time of immersion is required to observe the incorporation of dithiol molecules into the coating as well as the displacement of thiol molecules.     

Multi-walled carbon nanotube modified carbon paste electrode as an electrochemical sensor for the determination of epinephrine in the presence of ascorbic acid and uric acid

A biocompatible electrochemical sensor for selective detection of epinephrine (EP) in the presence of 1000-fold excess of ascorbic acid (AA) and uric acid (UA) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using a casting method. The electro-catalytic activity of the modified electrode for the oxidation of EP was investigated. The current sensitivity of EP was enhanced to about five times upon modification. A very minimum amount of modifier was used for modification. The voltammetric response of EP was well resolved from the responses of AA and UA. The electrochemical impedance spectroscopic (EIS) studies reveal the least charge transfer resistance for the modified electrode. The AA peak that is completely resolved from that of EP at higher concentrations of AA and the inability of the sensor to give an electrochemical response for AA below a concentration of 3.0 × 10^? 4 M makes it a unique electrochemical sensor for the detection of EP which is 100% free from the interference of AA. Two linear dynamic ranges of 1.0 × 10^? 4–1.0 × 10^? 5 and 1.0 × 10^? 5–5.0 × 10^? 7 M with a detection limit of 2.9 × 10^? 8 M were observed for EP at modified electrode. The practical utility of this modified electrode was demonstrated by detecting EP in spiked human blood serum and EP injection. The modified electrode is highly reproducible and stable with anti fouling effects.     

Sol–gel synthesis of tantalum oxide and phosphonic acid-modified carbon nanotubes composite coatings on titanium surfaces

Carbon nanotubes used as fillers in composite materials are more and more appreciated for the outstanding range of accessible properties and functionalities they generate in numerous domains of nanotechnologies. In the framework of biological and medical sciences, and particularly for orthopedic applications and devices (prostheses, implants, surgical instruments, …), titanium substrates covered by tantalum oxide/carbon nanotube composite coatings have proved to constitute interesting and successful platforms for the conception of solid and biocompatible biomaterials inducing the osseous regeneration processes (hydroxyapatite growth, osteoblasts attachment). This paper describes an original strategy for the conception of resistant and homogeneous tantalum oxide/carbon nanotubes layers on titanium through the introduction of carbon nanotubes functionalized by phosphonic acid moieties (P(O)(OH)₂). Strong covalent CP bonds are specifically inserted on their external sidewalls with a ratio of two phosphonic groups per anchoring point. Experimental results highlight the stronger “tantalum capture agent” effect of phosphonic-modified nanotubes during the sol–gel formation process of the deposits compared to nanotubes bearing oxidized functions (OH, CO, C(O)OH). Particular attention is also paid to the relative impact of the rate of functionalization and the dispersion degree of the carbon nanotubes in the coatings, as well as their wrapping level by the tantalum oxide matrix material. The resulting effect on the in vitro growth of hydroxyapatite is also evaluated to confirm the primary osseous bioactivity of those materials. Chemical, structural and morphological features of the different composite deposits described herein are assessed by X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission (TEM) electronic microscopies, energy dispersive X-rays analysis (EDX) and peeling tests.     

Induction heating vs conventional heating for the hydrothermal treatment of nitinol and its subsequent 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate coating by surface-initiated atom transfer radical polymerization

Nitinol is an alloy of great interest in general and especially in the biomedical field where many researches are aimed to improve both its corrosion resistance and its biocompatibility. In this work, we report on the advantage of an induction heating treatment in pure water compared to a conventional hydrothermal procedure. Both treatments lead to a hydroxylation of the surface, a decrease of the nickel amount in the outer part of the oxide layer, and a drastically decreased corrosion current density. However, the amount of surface hydroxyl groups is higher in the case of the induction heating treatment, which in turn leads to a denser grafting of atom transfer radical polymerization initiators and ultimately to a thicker 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate (MPC) polymer layer than in the case of conventional heating treatments. X-ray photoelectron spectroscopy (XPS), static contact angle, and polarization curves measurements as well as scanning electron microscopy (SEM) have been used to characterize the obtained modified surfaces.     

Electro-assisted assembly of aliphatic thiol, dithiol and dithiocarboxylic acid monolayers on copper

Molecular assemblies of organothiol molecules on polycrystalline copper surfaces are a well known process to confer them specific organizational and protective properties. In this paper, an original and promising approach is considered through an electro-assisted adsorption process via a cathodic polarization of the copper substrate. Spectroscopic characterizations (PM-IRRAS, XPS) and electrochemical studies (CV, LSV, cathodic desorption, SECM) highlight and confirm the benefits brought by this methodology in terms of resulting SAMs features and considerable savings of preparation time. In addition to normal alkylthiols with a monopod anchoring group, alkyldithiocarboxylic acid and alkyldithiol monolayers – both bipodal – are characterized with the prospect of forming either easier to remove or more adherent films, respectively.     

Microtribological and corrosion behaviors of 1H,1H,2H,2H-perfluorodecanethiol self-assembled films on copper surfaces

Fluoroorganic monolayers adsorped on copper are studied in terms of organization, structure, electrochemical behavior, corrosion and tribological properties. 1H,1H,2H,2H-perfluorodecanethiol thin films are grafted on copper via a self-assembling process. PM-IRRAS and XPS were used to investigate the organization, composition and structural properties of the SAMs. Cyclic voltammetry studies revealed a good oxidation blocking factor and polarization curves showed good anti-corrosion properties for the fluoroorganic film. However, these properties were inferior to those of n-dodecanethiol based SAMs. This was accounted for by the lower packing density and the larger number of defects of the 1H,1H,2H,2H-perfluorodecanethiol SAMs probably due to electrostatic and steric repulsion between fluorine atoms along the carbon chain and a number of CH₂ groups insufficient to permit good organization.Fluorine groups present in the monolayer of the fluoroorganic SAMs led to excellent lubricant properties for the ultrathin film. Surface wear resistance was also improved thanks to SAM grafting. 1H,1H,2H,2H-perfluorodecanethiol SAMs thus appear to be very interesting lubricants for copper as they improve surface mechanical properties by diminishing surface friction and wear.