Simple Method for the Preparation of Composites Based on PA6 and Partially Exfoliated Graphite

In the present work, the preparation of composite systems based on polyamide 6 (PA6) and exfoliated graphite was attempted by applying a simple procedure, which consists of a preliminary dispersion/exfoliation of graphite in the monomer, namely, ε- caprolactam (CL), and a subsequent polymerization of the above system. Atomic force microscopy (AFM) demonstrated specific interactions between CL and graphite surface. The dispersion of graphite in the monomer and polymer was assessed by scanning (SEM) and transmission (TEM) electron microscopy, while mechanical tests allowed to evaluate the influence of graphite on the polymer properties

On the use of hyperbranched aramids as support of Pt nanoparticles

AbstractA hyperbranched (HB) aromatic polyamide (aramid) synthesized from A2 (p-phenylenediamine) + B3 (trimesic acid) reactants has been used as Pt nanoparticle support. TEM measurements verified the possibility to obtain a high metallic dispersion (MD) using H2PtCl6 as metal precursor. The amount of Pt retained by the polymer support turned out to be lower than the Pd loading deposited on the same HB aramid from a different metal precursor, i.e. PdCl2, under the same exchange and reduction conditions, namely by the procedure reported in a previous paper of ours [1]. Moreover, Pt nanoparticle diameters have been found to depend on the reducing agent used. As compared to bubbling H2, NaBH4 allowed obtaining of metal particles characterized by smaller dimensions

Star-shaped furoate-PCL: An effective compound for the development of graphite nanoplatelets-based films

The aim of this study was to improve the dispersibility of graphite nanoplatelets (GNP) in films based on poly(ε-caprolactone) (PCL). To this end, a star-shaped PCL with furoate-like end groups (PCL-Fur), potentially capable of interacting/reacting with the surface of the graphene layers through Diels-Alder reactions, was synthesized by enzymatic catalysis. PCL-Fur was applied for film development by blending it with a commercial high molecular weight PCL (PCL-L) and GNP. The reactivity of GNP with respect to furoate groups was demonstrated by studying the thermal behavior of the GNP/methyl 2-furoate system, while the dispersibility of graphite in the solution containing PCL-Fur was studied by UV–Vis measurements. GNP proved to be well dispersed and adhered to the polymer matrix in the PCL-L/PCL-Fur/GNP composite films prepared by casting, in contrast to the films based on the neat PCL-L. This fine GNP dispersion resulted in films characterized by high electrical conductivity

A Novel Electrostimulated Drug Delivery System Based on PLLA Composites Exploiting the Multiple Functions of Graphite Nanoplatelets

A novel drug delivery system based on poly(l-lactide) (PLLA), graphite, and porphyrin was developed. In particular, 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (THPP) was chosen because, besides its potential as codispersing agent of graphite, it is a pharmacologically active molecule. Graphite nanoplatelets, homogeneously dispersed in both the neat PLLA and the PLLA/porphyrin films, which were prepared by solution casting, turned out to improve the crystallinity of the polymer. Moreover, IR measurements demonstrated that unlike PLLA/porphyrin film, where the porphyrin was prone to aggregate causing variable concentration throughout the sample, the system containing also GNP was characterized by a homogeneous dispersion of the above molecule. The effect of graphite nanoplatelets on the thermal stabilization, electrical conductivity, and improvement of mechanical properties of the polymer resulted to be increased by the addition of the porphyrin to the system, thus demonstrating the role of the molecule in ameliorating the filler dispersion in PLLA. The porphyrin release from the composite film, occurring both naturally and with the application of an electrical field, was measured using an UV-vis spectrophotometer. Indeed, voltage application turned out to improve significantly the kinetic of drug release. The biocompatibility of the polymer matrix as well as the mechanical and thermal properties of the composite together with its electrical response makes the developed material extremely promising in biological applications, particularly in the drug delivery field

Facile and Low Environmental Impact Approach to Prepare Thermally Conductive Nanocomposites Based on Polylactide and Graphite Nanoplatelets

In this work, the preparation of nanocomposites based on poly(l-lactide) PLLA and graphite nanoplatelets (GNP) was assessed by applying, for the first time, the reactive extrusion (REX) polymerization approach, which is considered a low environmental impact method to prepare polymer systems and which allows an easy scalability. In particular, ad hoc synthesized molecules, constituted by a pyrene end group and a poly(d-lactide) (PDLA) chain (Pyr-d), capable of interacting with the surface of GNP layers as well as forming stereoblocks during the ring-opening polymerization (ROP) of l-lactide, were used. The nanocomposites were synthesized by adding to l-lactide the GNP/initiator system, prepared by dispersing the graphite in the acetone/Pyr-d solution, which was dried after the sonication process. DSC and X-ray diffraction measurements evidenced the stereocomplexation of the systems synthesized by using the pyrene-based initiators, whose extent turned out to depend on the PDLA chain length. All the prepared nanocomposites, including those synthesized starting from a classical initiator, that is, 1-dodecanol, retained similar electrical conductivity, whereas the thermal conductivity was found to increase in the stereocomplexed samples. Preferential localization of stereocomplexed PLA close to the interface with GNP was demonstrated by scanning probe microscopy (SPM) techniques, supporting an important role of local crystallinity in the thermal conductivity of the nanocomposites

Star poly(ε-caprolactone)-based electrospun fibers as biocompatible scaffold for doxorubicin with prolonged drug release activity

Abstract In this work, a novel drug delivery system consisting of poly(e-caprolactone) (PCL) electrospun fibers containing an ad-hoc-synthesized star polymer made up of a poly(amido-amine) (PAMAM) core and PCL branches (PAMAM-PCL) was developed. The latter system which was synthesized via the ring opening polymerization of e-caprolactone, starting from a hydroxyl-terminated PAMAM dendrimer and characterized by means of 1H NMR, IR and DSC, was found to be compatible with both the polymer matrix and a hydrophilic chemotherapeutic drug, doxorubicin (DOXO), the model drug used in this work. The preparation of the dendritic PCL star product with an average arm length of 2000 g/mol was characterized using IR and 1H NMR measurements. The prepared star polymer possessed a higher crystallinity and a lower melting temperature than that of the used linear PCL. Electrospun fibers were prepared starting from solutions containing the neat PCL as well as the PCL/PAMAM-PCL mixture. Electrospinning conditions were optimized in order to obtain defect free fibers, which was proven by the structural FE-SEM study. PAMAM moieties enhanced the hydrophilicity of the fibers, as proved by comparing the water absorption for the PCL/PAMAM-PCL fibers to that neat PCL fibers. The drug-loaded system PCL/PAMAM-PCL was prepared by directly introducing DOXO into the electrospinning solutions. The DOXO-loaded PCL/PAMAM-PCL showed a prolonged release of the drug with respect to the DOXO-loaded PCL fibers and elicited effective controlled toxicity over A431 epidermoid carcinoma, HeLa cervical cancer cells and drug resistant MCF-7 breast cancer cells. On the contrary, the drug-free PCL/PAMAM-PCL scaffold demonstrated no toxic effects on human dermal fibroblasts, suggesting the biocompatibility of the proposed system which can be used in cellular scaffold applications

On the development of electrochemical sensors coated with polycaprolactone

The main aim of this study was to test the biopolymer polycaprolactone (PCL) as an electrode modifier for the electrochemical detection of dopamine (DA). PCL was chosen following a search for polymers with the appropriate geometry and functional groups for dopamine detection. The chemical structure and the average molecular weight of the synthesized PCL were determined by 1H-NMR, while DSC measurements showed a decrease in the crystallinity of a star-shaped polymer compared to a linear polymer. Atomic force microscopy and wettability tests performed on PCL-coated ITO electrodes demonstrated the influence of polymer architecture and functional groups on hydrophilicity and film morphology. Electrochemical studies revealed that electrodes coated with star polymers ending with carboxyl groups show good activity and selectivity, thus demonstrating the effectiveness and applicability of the developed sensors for the electrochemical detection of DA

Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures

The control of nanostructuration of graphene and graphene related materials (GRM) into self-assembled structures is strictly related to the nanoflakes chemical functionalization, which may be obtained via covalent grafting of non-covalent interactions, mostly exploiting π-stacking. As the non-covalent functionalization does not affect the sp2 carbon structure, this is often exploited to preserve the thermal and electrical properties of the GRM and it is a well-known route to tailor the interaction between GRM and organic media. In this work, non-covalent functionalization of graphite nanoplatelets (GnP) was carried out with ad-hoc synthesized pyrene-terminated oligomers of polylactic acid (PLA), aiming at the modification of GnP nanopapers thermal properties. PLA was selected based on the possibility to self-assemble in crystalline domains via stereocomplexation of complementary poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) enantiomers. Pyrene-initiated PLLA and PDLA were indeed demonstrated to anchor to the GnP surface. Calorimetric and X-ray diffraction investigations highlighted the enantiomeric PLAs adsorbed on the surface of the nanoplatelets self-organize to produce highly crystalline stereocomplex domains. Most importantly, PLLA/PDLA stereocomplexation delivered a significantly higher efficiency in nanopapers heat transfer, in particular through the thickness of the nanopaper. This is explained by a thermal bridging effect of crystalline domains between overlapped GnP, promoting heat transfer across the nanoparticles contacts. This work demonstrates the possibility to enhance the physical properties of contacts within a percolating network of GRM via the self-assembly of macromolecules and opens a new way for the engineering of GRM-based nanostructures

hydrogel based platforms to mimic in vivo drug diffusion a multicenter research

An airway mucus model is proposed thus serving as an in vitro screening tool with the aim to reduce the number of noneffective drugs reaching the preclinical trials. The engineered mucus model is an easy-to-use and easy-to-produce tool that can be easily coupled to state-of-art diffusion models and it is compatible with high throughput analysis. This platform will serve as the basis to implement the complexity of the model in terms of components, also including the effect of bacteri