Mohamed Jouini

Electrografted aryl diazonium initiators for surface-confined photopolymerization: a new approach to designing functional polymer coatings.

This article reports on the preparation of polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(2-hydroxyethyl methacrylate) (PHEMA) ultrathin grafts on gold substrates modified by 4-benzoylphenyl (BP) moieties derived from the electroreduction of the parent diazonium salt BF(4)(-), (+)N(2)-C(6)H(4)-CO-C(6)H(5) (DS). The grafted organic species -C(6)H(4)-CO-C(6)H(5) was found to be very effective in the surface-initiating photopolymerization (SIPP) of vinylic monomers in the presence of an aromatic tertiary amine co-initiator acting as a hydrogen donor. This novel tandem diazonium salt electroreduction/SIPP was found to be effective in grafting PS, PMMA, and PHEMA from the surface of gold-coated silicon wafers. The polymer films were characterized in terms of chemical structure and wettability by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy, and contact angle measurements, respectively. The polymer grafts were further evaluated as adsorbents for bovine serum albumin (BSA) used as a model protein. It was found gold/PHEMA resisted BSA adsorption because of its hydrophilic character, whereas PS and PMMA grafts adsorbed BSA via interfacial hydrophobic interaction. The XPS-determined extent of adsorbed BSA was found to increase linearly with the hydrophobic character of the polymer grafts as measured by water contact angles. This work shows that this novel tandem diazonium salt electroreduction/SIPP is a facile, ultrafast, efficient protocol for grafting polymer chains to surfaces. It broadens the enormous possibilities offered by aryl diazonium salts to generate functional organic coatings.

Host–guest complexation: a convenient route to polybithiophene composites by electrosynthesis in aqueous media. Synthesis and characterization of a new material containing cyclodextrins

An inclusion compound with hydroxypropyl-β-cyclodextrin (HPβCD) as host molecule has been used to electropolymerize bithiophene in aqueous medium. The complexation of bithiophene by HPβCD has been investigated by fluorescence, showing that BT molecules are tightly bound to cyclodextrin hosts. The electrochemical behaviour of this inclusion compound is irreversible in aqueous solution in the presence of HPβCD. The anodic electropolymerization of the BT–HPβCD complex has been performed in aqueous medium under galvanostatic or potentiodynamic conditions. Characterization of the deposited films supports the notion that polybithiophene (PBT) composites are formed. Although they show the usual features of PBT, the structure of the films appears to be considerably modified by the presence of cyclodextrins within the material but not grafted onto the polymeric backbone.

Solid-state dye-sensitized solar cells based on poly(3,4-ethylenedioxypyrrole) and metal-free organic dyes.

Poly(3,4-ethylenedioxypyrrole) (PEDOP), combined with metal-free organic sensitizers, is efficiently used for the first time as the hole-transporting material in solid-state dye-sensitized solar cells. Devices employing PEDOP as the hole conductor and D35 or D21 L6 as the sensitizer show a ten-times-higher energy-conversion efficiency (of 4.5% and 3.3%, respectively) compared to Ru-Z907-based devices. This is due to the efficient suppression of electron recombination.

New Blue-Photoluminescent Semi-Conducting Polymer Derived from Fluorinated Bisphenol A

A new confined p-phenylenevinylene (PPV)-type polymer (BPAF-PPV ) has been synthesized using Wittig condensation. The chemical structure of the polymer was well defined by 1H-NMR, 13C-NMR, and FT-IR spectroscopic analysis. BPAF-PPV contains oligomeric PPV units separated by hexafluoroisopropylidene groups in the main chain; it is fully soluble in common organic solvents and has a number-average molecular weight of 4570 g mol-1. Differential scanning calorimetry indicates that BPAF-PPV is amorphous and displays a glass transition temperature of 114 °C. The optical properties of the polymer were investigated by UV-visible absorption and photoluminescence spectroscopies. Its thin film showed a blue photoluminescence with a narrow emission spectrum. A high photoluminescence quantum efficiency of about 83% was determined in dilute solution. From the cyclic voltammetry analysis, the electrochemical bandgap was estimated to be 3.08 eV. A single-layer diode device of the configuration indium-tin oxide/ BPAF-PPV/aluminium has been fabricated and has a relatively low turn-on voltage of 3.0 V.

Electrochemical synthesis and characterization of thiophene conducting polymer in aqueous micellar medium

In opposite with the usually applied synthesis in organic media, the polymerization of bithiophene in aqueous media has been studied. The use of a non-ionic surfactant (polyoxyethylene octyl phenyl ether (Triton X-100)) is useful not only to solubilize the hydrophobic monomer but it is also important to incorporate various—biologically and catalytically active—additives. In this paper, the optimization of the polymerization conditions as well as the characterization of the electrochemical, spectral and mass exchange behavior of these composite films is summarized. The layers have shown imperceptible electroactivity in monomer-free aqueous LiClO4 solutions, and electrochemical quartz crystal microbalance (EQCM) studies exhibited scarce ion movements, caused assumingly by the fact that the dopant species—moving together with their hydrate shell in the aqueous media—could not penetrate into the hydrophobic film. In contrast, nice reversible redox transformation could be obtained in organic medium such as acetonitrile, where—according to the EQCM results—the charge carrier formation/depletion is accompanied by the incorporation/removal of ClO4− anions. In this solution, the spectral changes have proved the transformation into the conducting state, connected to both mono- and di-cation forms. The incorporation of the surfactant has been demonstrated by the extraordinary surface morphology of the polybithiophene (pBT) films, characterized by scanning electron microscopy. The elementary composition of the curious shell-shaped objects, monitored by energy dispersive X-ray spectroscopy (EDX), evidenced the presence of Triton X-100 by the increased C/S ratio compared to neat polybithiophene, while the Cl/S data reflected the changes connected to the doping level as a consequence of ClO4− anion movements. Moreover, ex situ attenuated total reflectance (ATR) FT–IR measurements clearly showed the existence of C―O bonds, also proving the successful functionalization by the surfactant, built permanently into the redox active films.

Electropolymerization of hydrophobic dipyrrolyls in aqueous medium based on inclusion chemistry

The host-guest complexation of hydrophobic dipyrrolyl monomers 1-4 with β-cyclodextrin has been studied in aqueous solution by means of 1 H NMR spectroscopy, chemical analysis and electrochemical techniques. In each case, 1:2 stoichiometry is found, the cyclodextrin cavities being likely located on the extremities of the monomers. Polymeric materials were obtained from such inclusion compounds in water by either electrochemical or chemical oxidation. ESCA and elemental analyses show that the host molecule is absent from these polymers, whose characteristics are quite similar to those synthesized in organic media. A scheme for polymerization in the presence of cyclodextrin is proposed.

Intervalence Charge Transfer in Mixed Valence Compound Modified by the Formation of a Supramolecular Complex.

The electrochemical and spectroelectrochemical properties of N,N-diphenyl-1,4-phenylenediamine (PDA) were investigated in the absence and in the presence of 18-crown-6-ether (18C6) or dibenzo 24-crown-8-ether (DB24C8), in a solution of tetrabutylammonium hexafluorophosphate (TBAPF6) in acetonitrile and in the presence of trifluoroacetic acid (TFA) only for 18C6. In neutral acetonitrile, PDA undergoes two reversible oxidation processes, which lead first to the formation of the cation-radical considered as mixed valence (MV) compound, and then to the dicationic species. When 18C6 is added in the medium and depending on 18C6 concentration, cyclic voltammetry shows a marked shift to more cathodic potentials of the current waves of the second redox process only. This is attributed to a strong interaction between the PDA(+2) dication and two 18C6 molecules, leading to the formation of a supramolecular complex with an association constant value K(a) = 7.0 × 10(7) M(-2). The interaction of 18C6 with PDA(+2) dication has a direct effect on the PDA(+.) cation-radical corresponding to a decrease in the lifetime of the MV compound and of the intramolecular electron transfer rate when 18C6 is present. Indeed, it results in a large decrease in the intervalence charge transfer (IV-CT) between the two amine centers in the MV compound (k(th) = 1.35 × 10(10) s(-1) in 18C6-free neutral solution containing 5.0 × 10(-4) M PDA, and k(th) = 3.6 × 10(9) s(-1) in the same medium at [18C6]/[PDA] = 20/1). And the comproportionation constant K(co) falls from 6.0 × 10(6) in 18C6-free solution to 1.6 × 10(3) at [18C6]/[PDA] = 20/1. In acidified acetonitrile and when TFA concentration is increased, PDA still shows the two successive and reversible oxidation processes, but both are shifted to more anodic potentials. However, when 18C6 is added, the two oxidation waves shift to more cathodic potentials, indicating an interaction of all protonated PDA redox states with 18C6, resulting in the formation of supramolecular complexes. In the presence of TFA, the value of K(co) is decreased to 4.3 × 10(4), but it remains unchanged when 18C6 is added, indicating no change in the lifetime of the MV compound. In this medium, IV-CT in the MV compound is greater with 18C6 (k(th) = 2.3 × 10(10) s(-1) for [18C6]/[PDA] = 20/1) than without (k(th) = 1.4 × 10(9) s(-1)), which indicates a more important IV-CT rate when 18C6 is present. The results show for the first time that is it possible to control the IV-CT rate, through the lifetime and the potential range where the MV compound is the most important. This control is not obtained as usual by chemical modification of the structure of the starting molecule, but by varying either the acidity or the 18C6 concentration as external stimuli, which lead to reversible formation/dissociation of a supramolecular complex species. Moreover, we also studied the electrochemical properties of PDA in the presence of wider crown ether such as DB24C8. We showed that PDA undergoes the same electrochemical behavior with DB24C8 than with 18C6 in neutral organic medium (K(a) = 2.9 × 10(3) M(-1)). This result suggests that the complexation between the electrogenerated PDA(+2) dication and the crown ethers may occur through face-to-face mode rather than rotaxane mode even with DB24C8 which is supposed to form inclusion complexes.

Poly(3′,4′-[bis(N,N′-ethyloxamyl)]terthiophene): A new functionalized conductive polymer with tunable pendent ethyloxamyl substituents

The electrosynthesis and the properties of a new functionalized polythiophene poly(3′,4′-[bis(N,N′-ethyloxamyl)]terthiophene) possessing a complexing cavity grafted onto one in three thiophene units are studied. The polymer has been characterized by means of several spectroscopic techniques (IR, Raman, XPS). It exhibits the usual behavior of the polythiophene class of material. Furthermore, it can be chemically modified, replacement of ester by amide groups in the solid state being evidenced by XPS and IR spectroscopy. The influence of the switching reaction of the polythiophene backbone upon the microscopic properties of the pendent ethyloxamyl groups is studied. IR spectroscopy and molecular modeling indicate that the π-electron density and the size of the complexing active center depend on the applied potential.