Polyaniline nanoparticles (PANI-NPs) were easily obtained applying the solvent displacement method by using N-methylpyrrolidone (NMP) as good solvent and water as poor solvent . Different polymers such as polyvinylpyrrolidone (PVP), chondroitin sulfate (ChS), polyvinyl alcohol (PVA), and polyacrylic acid (PAA) were used as stabilizers. Dynamic light scattering and scanning electron microscopy corroborated the size and morphology of the formed NPs. It was demonstrated that the size of nanoparticles could be controlled by setting the concentration of PANI in NMP, the NMP to water ratio, and the stabilizer’s nature. The functionalization and fluorescence of NPs were checked by spectroscopic techniques. Since polyaniline show only weak intrinsic luminescence, fluorescent groups were linked to the polyaniline chains prior to the nanoparticle formation using a linker. Polyaniline chains were functionalized by nucleophilic addition of cysteamine trough the thiol group thereby incorporating pendant primary aliphatic amine groups to the polyaniline backbone. Then, dansyl chloride (DNS-Cl), which could act as an extrinsic chromophore, was conjugated to the amine pendant groups. Later, the functionalized polyaniline was used to produce nanoparticles by solvent displacement. The optical and functional properties of fluorescent nanoparticles (F-PANI-NPs) were determined. F-PANI-NPs in the conductive state (pH < 4) are able to absorb near infrared radiation (NIR) creating a photothermal effect in an aqueous medium. Thus, multifunctional nanoparticles are obtained. The application of NIR on a F-PANI-NPs dispersion in contact with Pseudomonas aeruginosa causes bacterial death. Therefore, the F-PANI-NPs could be tracked and applied to inhibit different diseases caused by pathogenic microorganisms and resistant to antibiotics as well as a new disinfection method to surgical materials.
Organic chemical reactions have been used to functionalize preformed conducting polymers (CPs). The extensive work performed on polyaniline (PANI), polypyrrole (PPy), and polythiophene (PT) is described together with the more limited work on other CPs. Two approaches have been taken for the functionalization: (i) direct reactions on the CP chains and (ii) reaction with substituted CPs bearing reactive groups (e.g., ester). Electrophilic aromatic substitution, SEAr, is directly made on the non-conductive (reduced form) of the CPs. In PANI and PPy, the N-H can be electrophilically substituted. The nitrogen nucleophile could produce nucleophilic substitutions (SN) on alkyl or acyl groups. Another direct reaction is the nucleophilic conjugate addition on the oxidized form of the polymer (PANI, PPy or PT). In the case of PT, the main functionalization method was indirect, and the linking of functional groups via attachment to reactive groups was already present in the monomer. The same is the case for most other conducting polymers, such as poly(fluorene). The target properties which are improved by the functionalization of the different polymers is also discussed.
1 June 2010 in Colloids and Surfaces A: Physicochemical and Engineering Aspects
Two different approaches towards conjugated material (carbon nanotubes, conjugated polymers) functionalisation are presented: covalent bonding of functional groups and non covalent interaction with soluble polymers. Covalent functionalisation of carbon nanotubes is made by reaction of the aromatic ring with aryl radicals, produced by reduction of diazonium ions. In the case of conducting polymers, covalent functionalisation is brought about by reaction of polyanilines with diazotized aromatic amines (including amino terminated azo dyes). The non covalent functionalisation of carbon nanotubes is made by wrapping the nanotubes with soluble conducting polyanilines. The functionalised materials are characterised by FTIR spectroscopy, X-ray diffraction, dynamic light scattering, ultraviolet-visible absorption and emission spectroscopy, transmission electron microscopy, cyclic voltammetry, differential electrochemical mass spectroscopy and conductivity measurements. The materials are used to build ionic self assembled multilayers using a layer-by-layer deposition process. The charge transport and electrocatalytic behaviour of the assemblies, relevant to the application of the assemblies in nanostructured electrochemical biosensors, are evaluated using different redox molecules and/or its intrinsic electroactivity as probes.