The first study reports the development of a reusable, single-step system for the detection of specific substrates using oxidase-functionalized Fe3O4 nanoparticles (NPs) as a bienzyme system and using amplex ultrared (AU) as a fluorogenic substrate. In the presence of H2O2, the reaction pH between Fe3O4 NPs and AU was similar to the reaction of oxidase and the substrate. The catalytic activity of Fe3O4 NPs with AU was nearly unchanged following modification with poly(diallyldimethylammonium chloride) (PDDA). Based on these features, we prepared a composite of PDDA-modified Fe3O4 NPs and oxidase for the quantification of specific substrates through the H2O2-mediated oxidation of AU. By monitoring fluorescence intensity at 587 nm of oxidized AU, the minimum detectable concentrations of glucose, galactose, and choline were found to be 3, 2, and 20 £gM using glucose oxidase-Fe3O4, galactose oxidase-Fe3O4, and choline oxidase-Fe3O4 composites, respectively. The identification of glucose in blood was selected as the model to validate the applicability of this proposed method. The second study follows the first one. Using the catalytic activity of Fe3O4 NPs with AU to detect four kinds of neurotransmitter, such as dopamine, L-DOPA, adrenaline (epinephrine) and noradrenaline (norepinephrine). Because of there is specific interaction between Fe3O4 NPs and catecholamines (CAs), the Fe3O4 NPs will form CAs-Fe3O4 NPs composites in presence of CAs. The CAs on the Fe3O4 NPs surface must shelter the reaction between AU and H2O2, cause the fluorescence to be turned-off. The CAs just like a inhibitor, to inhibit the catalytic activity of Fe3O4 NPs. Therefore, we could use this inhibited system to detect the CAs compound concentration in the real sample.

Nous étudions la structure des solutions concentrées de polyélectrolytes (PE). Celle-ci n’a fait l’objet que de rares études expérimentales et aucun ordre d'orientation n'a jamais pu être observé dans les solutions de PE flexibles et semi-flexibles, bien que des travaux théoriques, basés sur l’approche d’Onsager, prévoient l'apparition d'une phase nématique aux fortes concentrations. Nous avons mesuré la position q* dans l'espace réciproque du pic présent dans la fonction de corrélation des solutions de PE fortement chargés obtenue par diffusion de rayonnement (DXPA et DNPA), et avons confronté sa variation avec la concentration c aux lois d'échelles théoriques q*~ca. Nous avons combiné des très fortes concentrations avec une haute résolution spatiale. La rigidité intrinsèque du PE est le paramètre clef de l’étude. En effet, le PSS, PE flexible, présente 3 régimes déjà connus : a=1/2 -régime semi-dilué- a=1/4 -régime concentré- un régime « ionomère » aux plus fortes concentrations pour lequel a=0. Le PDADMAC, PE semi-flexible, présente un comportement plus original puisque 4 régimes se succèdent : régimes semi-dilué et concentré avec a=1/2 et 1/4, puis deux régimes pour lesquels a=1 puis 1/2 qui sont totalement inédits. Le PaMSS, de rigidité intrinsèque intermédiaire, présente un comportement ambivalent, puisque les régimes semi-dilué et concentré précèdent un régime où a=1, puis un comportement « ionomère ». Nous introduisons un modèle simple permettant d'interpréter la succession des régimes a=1 puis 1/2 par l'apparition d'un ordre d'orientation. Nous discutons aussi les différences observées par DXPA et DNPA, et le rôle de la force ionique, variée par ajout de sel. / The structure of concentrated polyelectrolyte (PE) solutions is studied. There is a lack of experimental data on these systems. Specifically, no orientational order has ever been observed in solutions of flexible or semi-flexible PE, even though the existence of a nematic phase has been theoretically predicted at high concentration. We have measured the position q* in the reciprocal space of the peak that is present in the correlation function of aqueous solutions of highly charged PE, obtained by scattering measurements (SAXS and SANS). We combined high spatial resolution and a very wide concentration range to compare the variation of q* versus the concentration c, with the predicted scaling laws q*~ca. The intrinsic stiffness of PE is the key parameter of our study. Indeed, PSS, a flexible PE, exhibits 3 regimes already described: a=1/2 -semi-dilute regime- a=1/4 -concentrated regime- an “ionomeric” regime at extreme concentrations, for which a=0. PDADMAC is semi-flexible and exhibits a unique series of exponents involving 4 regimes: semi-dilute and concentrated regimes with a=1/2 and 1/4, followed by 2 regimes associated with a=1 and 1/2 respectively, which are new and unpredicted for PE solutions. PaMSS has an intermediate intrinsic stiffness, and exhibits hybrid behaviour. The semi-dilute and concentrated regimes are followed by an a=1 regime, and then an “ionomeric” regime for extreme concentrations. We introduce a simple model which explains the succession of the a=1 and 1/2 regimes as the appearance of an orientational order. We also discuss the differences between SAXS and SANS measurements, and the role played by the ionic strength, when salt is added.