Covalent grafting of chitosan onto stainless steel through aryldiazonium self-adhesive layers.

Although the conventional methods for strong attachment of chitosan onto stainless steel require many steps in different solvents, it has been demonstrated in this work that covalent grafting of chitosan on a steel surface can be easily achieved through the formation of a self-adhesive surface based on aryldiazonium seed layers. Initially, a polyaminophenyl layer is grafted on a stainless steel surface by means of the one-step GraftFast(TM) process (diazonium induced anchoring process). The grafted aminophenyl groups are then converted to an aryldiazonium seed layer by simply dipping the substrate in a sodium nitrite acidic solution. That diazonium-rich grafted layer can be used as a self-adhesive surface for subsequent spontaneous coating of chitosan onto the steel surface. X-ray photoelectron and impedance electrochemical spectroscopies were used to characterize the pristine and modified steel samples. As evidenced from impedance and linear polarization results, the primary polyaminophenyl layer characterized by a high charge transfer resistance contributed to better protection against corrosion of the resulting chitosan-coated steel in sulfuric acid medium.

Piezoelectric tuning fork probe for atomic force microscopy imaging and specific recognition force spectroscopy of an enzyme and its ligand.

Piezoelectric quartz tuning fork has drawn the attention of many researchers for the development of new atomic force microscopy (AFM) self-sensing probes. However, only few works have been done for soft biological materials imaging in air or aqueous conditions. The aim of this work was to demonstrate the efficiency of the AFM tuning fork probe to perform high-resolution imaging of proteins and to study the specific interaction between a ligand and its receptor in aqueous media. Thus, a new kind of self-sensing AFM sensor was introduced to realize imaging and biochemical specific recognition spectroscopy of glucose oxidase enzyme using a new chemical functionalization procedure of the metallic tips based on the electrochemical reduction of diazonium salt. This scanning probe as well as the functionalization strategy proved to be efficient respectively for the topography and force spectroscopy of soft biological materials in buffer conditions.

Versatile and nondestructive photochemical process for biomolecule immobilization.

Covalent immobilization of unmodified biological materials as proteins has been performed through a one-step and soft method. This process is based on a polyazidophenylene layer derived from the electroreduction of the parent salt 4-azidobenzenediazonium tetrafluoborate on gold substrates. The wavelength used (365 nm) for the photochemical grafting of a large variety of molecules as biomolecules is a key point to this nondestructive immobilization method. This simple process is also versatile and could be used for covalently binding a wide range of molecules such as polyethylene glycol moieties, for example. To validate this approach for biochip or microarray fabrication, a surface plasmon resonance imaging (SPRi) platform for immobilization of various antibody families was created by grafting G-protein through this process. This SPRi antibodies platform was tested with several consecutive cycles of antigen injections/regeneration steps without loss of activity.

3D amino-induced electroless plating: a powerful toolset for localized metallization on polymer substrates.

The "3D amino-induced electroless plating" (3D-AIEP) process is an easy and cost-effective way to produce metallic patterns onto flexible polymer substrates with a micrometric resolution and based on the direct printing of the mask with a commercial printer. Its effectiveness is based on the covalent grafting onto substrates of a 3D polymer layer which presents the ability to entrap Pd species. Therefore, this activated Pd-loaded and 3D polymer layer acts both as a seed layer for electroless metal growth and as an interdigital layer for enhanced mechanical properties of the metallic patterns. Consequently, flexible and transparent poly(ethylene terephtalate) (PET) sheets were selectively metalized with nickel or copper patterns. The electrical properties of the obtained metallic patterns were also studied.

Microscopic study of a ligand induced electroless plating process onto polymers.

The ligand induced electroless plating (LIEP) process was recently developed and thoroughly demonstrated with one of the most used polymers for plating processes: acrylonitrile-butadiene-styrene (ABS). This generic process is based, thanks to the use of diazonium salts as precursors, on the covalent grafting of a thin layer of poly(acrylic acid) (PAA) acting as ligand for metallic salts onto pristine polymer surfaces. This strategy takes advantage of the PAA ion exchange properties. Indeed, carboxylate groups contained in PAA allow one to complex copper ions which are eventually reduced and used as catalysts of the metallic deposition. Essentially based on ABS, ABS-PC (ABS-polycarbonate) and PA (polyamide) substrates, the present paper focuses on the role of the polymer substrate and the relationships between the macroscopic properties and microscopic characterizations such as infrared (IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The adhesion strength of the metallic layer deposited via that LIEP process with the bulk polymer substrates was successfully compared with the adhesion of similar copper films deposited by the usual process based on chromic acid etching and palladium-based seed layer, by measuring the T-peel adhesion strength, and by carrying out the common industrial scotch tape test. Lastly, the electrical properties of the deposited layer were studied thanks to a four-point probe and scanning tunneling microscopy (STM) measurements.

ABS polymer electroless plating through a one-step poly(acrylic acid) covalent grafting.

A new, efficient, palladium- and chromium-free process for the electroless plating of acrylonitrile-butadiene-styrene (ABS) polymers has been developed. The process is based on the ion-exchange properties of poly(acrylic acid) (PAA) chemically grafted onto ABS via a simple and one-step method that prevents using classical surface conditioning. Hence, ABS electroless plating can be obtained in three steps, namely: (i) the grafting of PAA onto ABS, (ii) the copper Cu(0) seeding of the ABS surface, and (iii) the nickel or copper metallization using commercial-like electroless plating bath. IR, XPS, and SEM were used to characterize each step of the process, and the Cu loading was quantified by atomic absorption spectroscopy. This process successfully compares with the commercial one based on chromic acid etching and palladium-based seed layer, because the final metallic layer showed excellent adhesion with the ABS substrate.

Surface homogeneity of anion exchange membranes: a chronopotentiometric study in the overlimiting current range.

Electrotransport of sodium chloride near and through the ASV anion exchange membrane was first investigated. Chronopotentiometric and current-voltage characteristics results have shown that the ASV membrane acts as a totally conducting plane with respect to the transport of NaCl electrolyte. SEM and AFM images contributed to confirm the overall homogeneous surface of the membrane. Further chronopotentiometric studies of the membrane were evaluated in the presence of different alkaline chloride solutions in order to explore the influence of alkali co-ions on the transport phenomena. Membrane characterization led to determine the transport number of chloride counterion in the membrane. It is reported in this work that chronopotentiometry using the Sand equation toward the homogeneous ion exchange membrane is a simple and efficient method for determination of the diffusion coefficient of the electrolytes in the bulk solution. Discussions on the transport properties of the electrolyte solutions in relation with the hydrated ion sizes allowed us to verify the diffusion coefficient of the electrolytes determined by means of chronopotentiometric method.

Monitoring the formation of TTF dimers by Na+ complexation.

The formation of the two dimeric species [(TTF)2]+* and (TTF+*)2 can be monitored by complexation of Na+ on a calix[4]arene-TTF assembly.

Molecule-to-metal bonds: electrografting polymers on conducting surfaces.

Electrografting is a powerful and versatile technique for modifying and decorating conducting surfaces with organic matter. Mainly based on the electro-induced polymerization of dissolved electro-active monomers on metallic or semiconducting surfaces, it finds applications in various fields including biocompatibility, protection against corrosion, lubrication, soldering, functionalization, adhesion, and template chemistry. Starting from experimental observations, this Review highlights the mechanism of the formation of covalent metal-carbon bonds by electro-induced processes, together with major applications such as derivatization of conducting surfaces with biomolecules that can be used in biosensing, lubrication of low-level electrical contacts, reversible trapping of ionic waste on reactive electrografted surfaces as an alternative to ion-exchange resins, and localized modification of conducting surfaces, a one-step process providing submicrometer grafted areas and which is used in microelectronics.

Univocal demonstration of the electrochemically mediated binding of Pb2+ by a modified surface incorporating a TTF-based redox-switchable ligand.

A tetrathiafulvalene-based redox-switchable ligand with unprecedented electrochemical recognition properties for a metallic cation is described and is chemically immobilized onto a solid surface. The recognition properties for Pb2+ are maintained at the solid-liquid interface. Evidence of the modulation of the binding affinity of the modified surface, as a function of the potential applied, is given by EQCM analyses and by direct measurements of residual Pb2+ concentration in solution by atomic absorption.