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The generation of filaments constituted by nanocomposites allows printing pieces with functional properties. A method is proposed for incorporating nanoparticles in plastic filaments (thermoplastic polyurethane, PU) by diffusion in the swollen material. The nanoparticles must be dispersed in solvents (or solvent mixtures) in which the polymer swells but does not dissolve. Nanoparticles are incorporated mainly at the surface as revealed by SEM/EDS mapping. The thermal properties (studied by DSC and TGA) of the PU are only slightly affected by the presence of NPs. Test pieces successfully are printed using the modified filaments. Incorporation of solid lubricant (MoS2) nanoparticles decreases the coefficient of friction of the printed test samples.

PNIPAM hydrogels are widely studied materials which swell in a great extent in water and water like solvents (e.g. alcohols). The hydrophilic nature of PNIPAM networks is very attractive however it is an important disadvantage at the moment of encapsulating hydrophobic drugs, which minimize their use in other fields. In this work we studied the swelling in different solvent mixtures with water and also in pure nonaqueous solvents, some of them immiscible with water. Accordingly, PNIPAM gels swell strongly in highly polar solvents (e.g. chloroform) but it does not swell in slightly polar solvents (e.g.Toluene). The main interaction between the solvent and the polymer chain seems to involve the hydrogen bonding with the amide group, according to the calculated Hansen parameters (δh). It is possible to swell the gel in binary or ternary mixtures containing toluene. In that way, non-polar substances can be loaded inside the gel to change its properties. As a proof of concept, polyaniline (PANI) solubilized in chloroform using camphorsulfonate as solubilizing counterion. The obtained nanocomposites become sensitive to pH changing color and conductivity when exposed to basic or acidic aqueous solutions. Fil: Martinez, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina Fil: Molina, María Alejandra. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina Fil: Bongiovanni Abel, Silvestre Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Barbero, César Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina

Polymeric nanocomposites were obtained by the formation of a thermosensitive hydrogel matrix around conducting polymer (CP) nanoparticles. The CP is able to absorb electromagnetic radiation which is converted into heat and induces the phase transition of the surrounding hydrogel. The method chosen to form the hydrogel is the free radical polymerization of a copolymer (N-isopropylacrylamide (NIPAM) and 2-acrylamide-2-methylpropano sulfonic acid (AMPS), PNIPAM-co-2% AMPS) in the presence of bisacrylamide as the crosslinker. The nanoparticles are polypyrrole nanospheres (PPy NP), polyaniline nanofibers (PANI NF), and polyaniline nanospheres (PANI NP). The morphology of the composites was studied using SEM microscopy and the percentage composition of each material was evaluated by thermogravimetric analysis (TGA). The swelling equilibrium capacity and rate are clearly affected by the nanoparticle shape and nature. However, the nanocomposites LCST are similar to that of the matrix. Upon RF irradiation, the three nanocomposites increase the temperature and reach the LCST after 320 seconds of irradiation (320 kJ). Upon MW application, the local temperature reaches the LCST after only 30 s (21 kJ), resulting in a MW more effective than RF to drive the transition. These results demonstrate that the proposed materials are useful as a remotely driven actuator. Fil: Bongiovanni Abel, Silvestre Manuel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Rivarola, Claudia Rosana. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Barbero, César Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Molina, María Alejandra. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina

A method for the synthesis of a linear block copolymer (PNIPAM-b-PANI), containing a thermoresponsive block (poly(N-isopropylacrylamide), PNIPAM) and a Near Infrared (NIR) light-absorbing block (polyaniline, PANI), is reported. The synthetic approach involves a two-step successive polymerization reaction. First, the radical polymerization of NIPAM is done using 4-aminothiophenol as a chain transfer agent for the obtention of thermosensitive block terminated with an aniline (ANI) moiety. Second, the oxidative polymerization of ANI is initiated in ANI moiety of thermosensitive block to grow the second conductive PANI block. 1H nuclear magnetic resonance (NMR) and FT-IR spectroscopy shows the characteristics peaks of both polymeric blocks revealing the successful copolymerization process. Static Light Scattering (SLS) and UV-Visible combined measurements allowed the determination of the Mw for PNIPAM-b-PANI macromolecule: 5.5 &times, 105 g mol&minus, 1. The resulting copolymer is soluble in water (8.3 g L&minus, 1) and in non-aqueous solvents, such as ethanol, formic acid, acetonitrile, and others. Both polymer blocks chains show the properties of the polymer chains. The block copolymer shows a lower critical solution temperature (LCST) at the same temperature (32&ndash, 34 &deg, C) than PNIPAM, while the copolymer shows pH dependent UV-vis-NIR absorption similar to PANI. The PNIPAM block suffers a coil to globule transition upon NIR light irradiation (785 nm, 100 mW), as shown by turbidimetry and Atomic Force Microscopy (AFM), due to local heating (more than 9 &deg, C in 12 min) induced by the NIR absorption at the PANI block. Furthermore, the electrical conductivity of PNIPAM-b-PANI thin films is demonstrated (resistivity of 5.3 &times, 10&minus, 4 &Omega, &minus, 1 cm&minus, 1), indicating that the PANI block is present in its conductive form.

Resistive sensors for organic vapors were made usingpolyaniline (PANI) and functionalized PANI as thin films ordeposits of PANI nanofibers. PANI thin films were synthesized byin situ chemical polymerization onto flat polyethylene films. PANInanofibers were produced by interfacial polymerization. Bothpolymeric materials were chemically modified through aromaticelectrophilic substitution or nucleophilic addition and used asactive materials in resistive sensors. The analysis of the resistancetimesensor profiles suggested that chemical modification affectsstrongly the sensor response. Moreover, the magnitude, the sign,and the rate of the sensor response showed differences for activematerials with the same chemical structure and differentmorphology. It is demonstrated that using only one conductingpolymer but creating material diversity by chemicalfunctionalization or morphological changes different sensorsresponses for the same volatiles can be obtained. This behaviorallows a simple way to produce sensors arrays which can be usedin electronic noses. Fil: Bongiovanni Abel, Silvestre Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Olejnik, Robert. Univerzita Tomase Bati Ve Zline; República Checa Fil: Rivarola, Claudia Rosana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Slobodian, Petr. Univerzita Tomase Bati Ve Zline; República Checa Fil: Saha, Petr. Univerzita Tomase Bati Ve Zline; República Checa Fil: Acevedo, Diego Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Barbero, César Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina

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.

The development of three-dimensional (3D) scaffolds with physical and chemical topological cues at the macro-, micro-, and nanometer scale is urgently needed for successful tissue engineering applications. 3D scaffolds can be manufactured by a wide variety of techniques. Electrospinning technology has emerged as a powerful manufacturing technique to produce non-woven nanofibrous scaffolds with very interesting features for tissue engineering products. However, electrospun scaffolds have some inherent limitations that compromise the regeneration of thick and complex tissues. By integrating electrospinning and other fabrication technologies, multifunctional 3D fibrous assemblies with micro/nanotopographical features can be created. The proper combination of techniques leads to materials with nano and macro-structure, allowing an improvement in the biological performance of tissue-engineered constructs. In this review, we focus on the most relevant strategies to produce electrospun polymer/composite scaffolds with 3D architecture. A detailed description of procedures involving physical and chemical agents to create structures with large pores and 3D fiber assemblies is introduced. Finally, characterization and biological assays including in vitro and in vivo studies of structures intended for the regeneration of functional tissues are briefly presented and discussed.

Photo-thermo-mechanochemical (P-T-MCh) nanocomposites provide a mechanical and/or chemical output (MCh) in response to a photonic (P) input, with the thermal (T) flux being the coupling factor. The nanocomposite combines a photon absorbing nanomaterial with a thermosensitive hydrogel matrix. Conjugated (absorbing in the near infrared (NIR, 750&ndash, 850 nm) wavelength range) polymer (polyaniline, PANI) nanostructures are dispersed in cross-linked thermosensitive (poly(N-isopropylacrylamide), PNIPAM) hydrogel matrices, giving the nanocomposite P-T-MCh properties. Since PANI is a conductive polymer, electromagnetic radiation (ER) such as radiofrequency (30 kHz) and microwaves (2.4 GHz) could also be used as an input. The alternating electromagnetic field creates eddy currents in the PANI, which produces heat through the Joule effect. A new kind of &ldquo, product&rdquo, nanocomposite is then produced, where ER drives the mechanochemical properties of the material through thermal coupling (electromagnetic radiation thermomechanochemical, ER-T-MCh). Both optical absorption and conductivity of PANI depend on its oxidation and protonation state. Therefore, the ER-T-MCh materials are able to react to the surroundings properties (pH, redox potential) becoming a smart (electromagnetic radiation thermomechanochemical) (sER-T-MCh material. The volume changes of the sER-T-MCh materials are reversible since the size and shape is recovered by cooling. No noticeable damage was observed after several cycles. The mechanical properties of the composite materials can be set by changing the hydrogel matrix. Four methods of material fabrication are described.

Conductive polyaniline nanoparticles (PANI NPs) are synthesized by oxidation of aniline with persulfate in acid media, in the presence of polymeric stabilizers: polyvinilpyrrolidone (PVP), poly(N-isopropylacrylamide) (PNIPAM), and hydroxylpropylcellulose (HPC). It is observed that the size of the nanoparticles obtained depends on the polymeric stabilizer used, suggesting a mechanism where the aggregation of polyaniline molecules is arrested by adsorption of the polymeric stabilizer. Indeed, polymerization in the presence of a mixture of two polymers having different stabilizing capacity (PVP and PNIPAM) allows tuning of the size of the nanoparticles. Stabilization with biocompatible PVP, HPC and PNIPAM allows use of the nanoparticle dispersions in biological applications. The nanoparticles stabilized by thermosensitive polymers (PNIPAM and HPC) aggregate when the temperature exceeds the phase transition (coil to globule) temperature of each stabilizer (Tpt = 32 °C for PNIPAM or Tpt = 42 °C for HPC). This result suggests that an extended coil form of the polymeric stabilizer is necessary to avoid aggregation. The dispersions are reversibly restored when the temperature is lowered below Tpt. In that way, the effect could be used to separate the nanoparticles from soluble contaminants. On the other hand, the PANI NPs stabilized with PVP are unaffected by the temperature change. UV-visible spectroscopy measurements show that the nanoparticle dispersion changes their spectra with the pH of the external solution, suggesting that small molecules can easily penetrate the stabilizer shell. Near infrared radiation is absorbed by PANI NPs causing an increase of their temperature which induces the collapse of the thermosensitive polymer shell and aggregation of the NPs. The effect reveals that it is possible to locally heat the nanoparticles, a phenomenon that can be used to destroy tumor cells in cancer therapy or to dissolve protein aggregates of neurodegenerative diseases (e.g. Alzheimer). Moreover, the long range control of aggregation can be used to modulate the nanoparticle residence inside biological tissues. Fil: Bongiovanni Abel, Silvestre Manuel. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Molina, María Alejandra. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Rivarola, Claudia Rosana. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Kogan, Marcelo Javier. Universidad de Chile; Chile Fil: Barbero, César Alfredo. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina