Detection of DNA hybridization by ABEI electrochemiluminescence in DNA-chip compatible assembly.

The electrochemiluminescence (ECL) of a luminol derivate (ABEI) generated both by a carbon electrode and a polypyrrole-coated carbon electrode was examined. It was found that the polypyrrole film (ppy) did not inhibit the ECL. After that, ABEI anchored on a single stranded DNA target (ODNt) has been used for the ECL detection of the hybridization between a complementary single stranded DNA probe (ODNp) covalently linked to a polypyrrole support and the ODNt. The ECL detection has been performed using a DNA sensor having a low surface concentration of ODNp probes, constituted of a polypyrrole copolymer electrosynthesized from a pyrrole-ODNp/pyrrole monomer ratio of 1/20,000.

Oligothiophene bipyridine alternate copolymers and their ruthenium metalated analogues: in situ ESR and UV-vis investigations of metal-chain interactions.

In situ electron spin resonance (ESR) and UV-vis spectro-electrochemical studies have been performed on two copolymers consisting of alternating subunits of regioregular head to tail (HT) coupled 3-octylthiophene tetramer and 2,2'-bipyridine subunits (P4) or 3-octylthiophene hexamer subunits of the same regioregularity and 2,2'-bipyridine subunits (P6). Both P4 and P6 have been investigated in their metal-free form as well as in the ruthenium(II) metalated form (P4-Ru and P6-Ru). P4 and P6 in the p-doped state exhibit a clear ESR signal characteristic of the presence of polarons in the oligothienylene subunits. In the case of P4, no recombination of polarons into bipolarons is observed, whereas the recombination process takes place in P6. The formation of bipolarons is well-rationalized in terms of the conjugation length, and it seems clear that the higher length of the oligothiophene subunit in P6( )()stabilizes bipolarons(.)() The same effect, is induced by the coordination of -Ru(bpy)(2)(2+) to the bipyridine unit in the metalated form of both polymers, which results in an increase of the conjugation length. Important information is gained from the analysis of the ESR spectra of both nonmetalated and metalated in the oxidized (p-doped) and reduced (n-doped) forms. In the p-doped state both nonmetalated and metalated polymers reveal the presence of a narrow ESR line characteristic of the mobile spin carriers in the polymer matrix. The oxidation of the metal center occurs at higher potentials and leads to an irreversible destruction of the system. To the contrary, in the reduced (n-doped) state the ESR lines of the nonmetalated and metalated polymers markedly differ. A significant line broadening with simultaneous change of the g-value is caused by spin-orbit coupling phenomenon induced by the presence of the coordinating metal. Finally, the observation of a clear polaronic band in the UV-vis spectrum of p-doped P4 and its strong dependence on the applied potential can be clearly correlated with the potential induced changes in the ESR spin density. The same applies to P4-Ru, where the changes in the polaronic and bipolaronic bands can also be correlated with the ESR spin density changes.

Comparison by QCM and photometric enzymatic test of the biotin-avidin recognition on a biotinylated polypyrrole.

By gravimetric measurements using a quartz cristal microbalance (QCM), we have studied the immobilization of biotinylated glucose oxidase enzymes (B-GOx) bound through on an intermediate avidin layer to a biotinylated polypyrrole film. The aim is to assess the amount of B-GOx specifically anchored on the biotinylated polypyrrole/avidin assembly thank to the biotin/avidin interaction between avidin and B-GOx. Indeed the estimated amount from the QCM measurement corresponds to the specific recognition of avidin/B-GOx added to a non-specific recognition (adsorption) of B-GOx. In order to discriminate these two phenomena, we have carried out a study by QCM of the anchoring of B-GOx on an avidin layer linked by adsorption to a polypyrrole free from biotin units. From QCM measurements we have deduced for the biotinylated polypyrrole/avidin assembly that the amount of B-GOx bound via the biotin/avidin interaction and those due to the avidin adsorption process correspond to 3.9 pmol cm(-2) (1.3 equivalent of B-Gox monolayer) and 1.4 pmol cm(-2) (0.46 equivalent of B-GOx monolayer) respectively. These values have been corroborated by measurements of the enzymatic activity of GOx.

Photophysics and electron transfer in poly(3-octylthiophene) alternating with Ru(II)- and Os(II)-bipyridine complexes.

A series of soluble metal-organic polymers that contain Ru(II)- and Os(II)-polypyridine complexes interspersed within a pi-conjugated poly(3-octylthiophene) backbone are prepared. Detailed electrochemical and photophysical studies are carried out on the polymers and two model complexes to determine the extent that the metal-polypyridine units interact with the pi-conjugated system. The results indicate that there is a strong electronic interaction between the metal-based chromophores and the pi-conjugated organic segments, and consequently the photophysical properties are not simply based on the sum of the properties of the individual components. In the Ru(II) polymers, the metal-to-ligand charge-transfer (MLCT) excited state is slightly higher in energy than the 3 pi,pi* state of the poly(3-octylthiophene) backbone. This state ordering results in a material that displays only a weak MLCT luminescence and a long-lived transient absorption spectrum that is dominated by the 3 pi,pi* state. In the Os(II) polymer the MLCT state is lower in energy than the polythiophene-based 3 pi,pi* state and the "unperturbed" MLCT emission is observed. Finally, all of the metal-organic polymers undergo photoinduced bimolecular electron-transfer (ET) reactions with the oxidative quencher dimethyl viologen. Transient absorption spectroscopy reveals that photoinduced ET to dimethyl viologen produces the oxidized polymers, and in most cases, the transient spectra are dominated by features characteristic of a poly(3-octylthiophene) polaron.