Synthesis of core-shell Au@polypyrrole nanocomposite using a dendrimer-template approach

Conducting polymeric nanostructures have been reported recently, which were produced from polypyrrole (PPy), including hollow nanocapsules, nanofibers, nanoporous membranes, nanowires, and nanofilms. In most cases, new synthetic routes were used aimed at controlling specific properties of these conducting nanostructures at the molecular level. In this communication we present a new chemical route to synthesize polypyrrole-based nanocomposites, in which polyamidoamine (PAMAM) dendrimers encapsulating Au nanoparticles are used as template. The two-step synthesis comprises the reduction of Au nanoparticles inside PAMAM molecules followed by PPy polymerization around the PAMAM-Au nanoparticles. The structure of the core-shell PAMAM-gold@polypyrrole nanospheres comprises a 40 nm PPy shell enclosing a core of 3 nm gold nanoparticles, as revealed by Transmission Electronic Microscopy (TEM). This new, environmentally-friendly approach may be suitable to produce hybrid nanomaterials for applications in catalysis, batteries, sensors, and micro/nanoelectronic devices.     

Immobilization of ibuprofen-containing nanospheres in layer-by-layer films

Liposomes have been applied to many fields as nanocarriers, especially in drug delivery as active molecules may be entrapped either in their aqueous interior or onto the hydrophobic surface. In this paper we describe the fabrication of layer-by-layer (LbL) films made with liposomes incorporating the anti-inflammatory ibuprofen. The liposomes were made with dipalmitoyl phosphatidyl choline (DPPC), dipalmitoyl phosphatidyl glycerol (DPPG) and palmitoyl oleoyl phosphatidyl glycerol (POPG). LbL films were assembled via alternate adsorption of the polyamidoamine dendrimer (PAMAM), generation 4, and liposomes containing ibuprofen. According to dynamic light scattering measurements, the incorporation of ibuprofen caused DPPC and DPPG liposomes to become more stable, with a decrease in diameter from 140 to 74 nm and 132 to 63 nm, respectively. In contrast, liposomes from POPG became less stable, with an increase in size from 110 to 160 nm after ibuprofen incorporation. These results were confirmed by atomic force microscopy images of LbL films, which showed a large tendency to rupture for POPG liposomes. Film growth was monitored using nanogravimetry and UV-Vis spectroscopy, indicating that growth stops after 10 bilayers. The release of ibuprofen obtained with fluorescence measurements was slower for the liposomes, with decay times of 9.2 and 8.5 h for DPPG and POPG liposomes, respectively, than for the free drug with a decay time of 5.2 h. Ibuprofen could also be released from the LbL films made with DPPG and POPG liposomes, which is promising for further uses in patches.     

Multi-walled carbon nanotubes and poly(lactic acid) nanocomposite fibrous membranes prepared by solution blow spinning

Nanocomposite fibers based on multi-walled carbon nanotubes (MWCNT) and poly(lactic acid) (PLA) were prepared by solution blow spinning (SBS). Fiber morphology was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). Electrical, thermal, surface and crystalline properties of the spun fibers were evaluated, respectively, by conductivity measurements (4-point probe), thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), contact angle and X-ray diffraction (XRD). OM analysis of the spun mats showed a poor dispersion of MWCNT in the matrix, however dispersion in solution was increased during spinning where droplets of PLA in solution loaded with MWCNT were pulled by the pressure drop at the nozzle, producing PLA fibers filled with MWCNT. Good electrical conductivity and hydrophobicity can be achieved at low carbon nanotube contents. When only 1 wt% MWCNT was added to low-crystalline PLA, surface conductivity of the composites increased from 5 x 10(-8) to 0.46 S/cm. Addition of MWCNT can slightly influence the degree of crystallinity of PLA fibers as studied by XRD and DSC. Thermogravimetric analyses showed that MWCNT loading can decrease the onset degradation temperature of the composites which was attributed to the catalytic effect of metallic residues in MWCNT. Moreover, it was demonstrated that hydrophilicity slightly increased with an increase in MWCNT content. These results show that solution blow spinning can also be used to produce nanocomposite fibers with many potential applications such as in sensors and biosensors.     

Melt processing of composites of PVDF and carbon black modified with conducting polymers

Conductive composites from poly(vinylidene fluoride) (PVDF) and a novel thermally stable conductive additive made via in situ deposition of polyaniline or polypyrrole on carbon black particles were produced by a melting process. Electrical conductivity in the order of 10^?2 S/cm could be achieved with low contents of the conductive filler. Thermogravimetric analysis (TGA) showed that there is no appreciable degradation of the composites at temperatures as high as 300°C. Moreover, the addition of the conducting polymer‐modified carbon black additive is advantageous to the melt processing of the composites, reducing the melt viscosity in comparison to the addition of pure carbon black. Composites containing the β‐phase of PVDF could be obtained via quenching from the melt, as indicated by X‐Ray diffraction analysis. The type and amount of the additive and the quenching rate influence the formation of β‐phase in the PVDF composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 553–557, 2004     

Effects of different complexing agents on the physical properties of ZnO nanoparticles

ZnO nanoparticles have been synthesised via a co-precipitation method using different complexing agents. X-ray diffraction (XRD) analysis revealed that ZnO nanoparticles were composed of a single hexagonal wurtzite phase. Transmission electron microscopy (TEM) analysis indicates that the samples prepared without any complexing agent have slight agglomeration characteristics presenting a prismatic morphology and a wider size distribution from 22 to 72?nm, which provides good material packing density. However, samples synthesised using urea and glycine are similar and show spherical-like morphology. XRD and TEM analyses indicate that complexing agents also have an important role in the size of the ZnO nanoparticles, where the average particle size of 47 and 22?nm were obtained using urea and glycine, respectively.     

Elastomeric conductive composites based on conducting polymer–modified carbon black

Thermally stable elastomeric composites were prepared via melt processing from poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) and conducting polymer-modified carbon black (CPMCB) additives. CPMCB additives represent a novel thermally stable conductive compound made via “in-situ” deposition of polyaniline or polypyrrole on carbon black particles. Incorporating CPMCB is advantageous to the melt processing of composites, as it reduces the melt viscosity in comparison to the use of pure carbon black. Thermogravimetric analyses (TGA) showed that the composites are thermally stable with no appreciable degradation at temperatures as high as 300°C. In addition, the electrical conductivity of the composites was found to be very stable at high temperatures. Polym. Compos. 25:617–621, 2004. © 2004 Society of Plastics Engineers.     

Contribution of the cashew gum (Anacardium occidentale L.) for development of layer-by-layer films with potential application in nanobiomedical devices

The search for bioactive molecules to be employed as recognition elements in biosensors has stimulated researchers to pore over the rich Brazilian biodiversity. In this sense, we introduce the use of natural cashew gum (Anacardium occidentale L.) as an active biomaterial to be used in the form of layer-by-layer films, in conjunction with phthalocyanines, which were tested as electrochemical sensors for dopamine detection. We investigated the effects of chemical composition of cashew gum from two different regions of Brazil (Piauí and Ceará states) on the physico-chemical characteristics of these nanostructures. The morphology of the nanostructures containing cashew gum was studied by atomic force microscopy which indicates that smooth films punctuated by globular features were formed that showed low roughness values. The results indicate that, independent of the origin, cashew gum stands out as an excellent film forming material with potential application in nanobiomedical devices as electrochemical sensors.     

Tailoring molecular architectures with cobalt tetrasulfonated phthalocyanine: immobilization in layer-by-layer films and sensing applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.     

Highly stable, edible cellulose films incorporating chitosan nanoparticles

The need for biodegradable polymers for packaging has fostered the development of novel, biodegradable polymeric materials from natural sources, as an alternative to reduce amount of waste and environmental impacts. The present investigation involves the synthesis of chitosan nanoparticles-carboxymethylcellulose films, in view of their increasing areas of application in packaging industry. The entire process consists of 2-steps including chitosan nanoparticles preparation and their incorporation in carboxymethylcellulose films. Uniform and stable particles were obtained with 3 different chitosan concentrations. The morphology of chitosan nanoparticles was tested by transmission electron microscopy, revealing the nanoparticles size in the range of 80 to 110 nm. The developed film chitosan nanoparticles-carboxymethylcellulose films were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis, solubility tests, and mechanical analysis. Improvement of thermal and mechanical properties were observed in films containing nanoparticles, with the best results occurring upon addition of nanoparticles with 110 nm size in carboxymethylcellulose films. PRACTICAL APPLICATION: Carboxymethylcellulose films containing chitosan nanoparticles synthesized and characterized in this article could be a potential material for food and beverage packaging applications products due to the increase mechanical properties and high stability. The potential application of the nanocomposites prepared would be in packaging industry to extend the shelf life of products.     

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes,chitosan and cobalt (II) phthalocyanine

The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc}_n and {Chit-SWCNTs/CoTsPc}_n (n = 1–10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E_1/2 at −0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]⁵⁻/[CoTsPc(II)]⁴⁻ and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc}₅ multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.