PET/Graphene Nanocomposite Fibers Obtained by Dry-Jet Wet-Spinning for Conductive Textiles.

The combination of polyethylene terephthalate (PET), one of the most used polymers in the textile industry, with graphene, one of the most outstanding conductive materials in recent years, represents a promising strategy for the preparation of conductive textiles. This study focuses on the preparation of mechanically stable and conductive polymer textiles and describes the preparation of PET/graphene fibers by the dry-jet wet-spinning method from nanocomposite solutions in trifluoroacetic acid. Nanoindentation results show that the addition of a small amount of graphene (2 wt.%) to the glassy PET fibers produces a significant modulus and hardness enhancement (≈10%) that can be partly attributed to the intrinsic mechanical properties of graphene but also to the promotion of crystallinity. Higher graphene loadings up to 5 wt.% are found to produce additional mechanical improvements up to ≈20% that can be merely attributed to the superior properties of the filler. Moreover, the nanocomposite fibers display an electrical conductivity percolation threshold over 2 wt.% approaching ≈0.2 S/cm for the largest graphene loading. Finally, bending tests on the nanocomposite fibers show that the good electrical conductivity can be preserved under cyclic mechanical loading.

Injectable hybrid hydrogels physically crosslinked based on carrageenan and green graphene for tissue repair.

Injectable and biocompatible novel hybrid hydrogels based on physically crosslinked natural biopolymers and green graphene for potential use in tissue engineering are reported. Kappa and iota carrageenan, locust bean gum and gelatin are used as biopolymeric matrix. The effect of green graphene content on the swelling behavior, mechanical properties and biocompatibility of the hybrid hydrogels is investigated. The hybrid hydrogels present a porous network with three-dimensionally interconnected microstructures, with lower pore size than that of the hydrogel without graphene. The addition of graphene into the biopolymeric network improves the stability and the mechanical properties of the hydrogels in phosphate buffer saline solution at 37 °C without noticeable change in the injectability. The mechanical properties of the hybrid hydrogels were enhanced by varying the dosage of graphene between 0.025 and 0.075 w/v%. In this range, the hybrid hydrogels preserve their integrity during mechanical test and recover the initial shape after removing the applied stress. Meanwhile, hybrid hydrogels with graphene content of up to 0.05 w/v% exhibit good biocompatibility for 3T3-L1 fibroblasts; the cells proliferate inside the gel structure and show higher spreading after 48 h. These injectable hybrid hydrogels with graphene have promising future as materials for tissue repair.

Designing New Sustainable Polyurethane Adhesives: Influence of the Nature and Content of Diels-Alder Adducts on Their Thermoreversible Behavior.

With a view to the development of new sustainable and functional adhesives, two Diels-Alder (DA) adducts are incorporated as a third component into the curing process of solvent-based and solvent-free polyurethanes in this study. The influence of the nature and content of the DA molecules on the retro-DA (rDA) reaction and its reversibility and cyclability is investigated. It is demonstrated that the bonding/debonding properties of the adhesives are mainly controlled by the concentration of the DA adducts, with a minimum thermoreversible bond (TB) content required that depends on the system and the total ratio between all the diols in the formulation. For the solvent-based system, rDA/DA reversibility can be repeated up to ~20 times without deterioration, in contrast to the solvent-free system where a gradual loss in the DA network reconstruction efficiency is observed. Despite this limitation, the solvent-free system presents clear advantages from an environmental point of view. The changes observed in the physical properties of these new thermoreversible adhesives are of great relevance for recycling strategies and, in particular, their potential for separating multilayered film packaging materials in order to recycle the individual polymer films involved.

Understanding the Reinforcement of Graphene in Poly(Ether Ether Ketone)/Carbon Fibre Laminates.

PEEK appears as an excellent candidate to substitute epoxy resins in carbon fibre laminates for high-performance aeronautical applications. The optimization of the properties and, in particular, of the transition region between the fibres and the matrix appear as a major issue prior to serial production. Graphene, modified with two compatibilizers, has been incorporated in the polymer layer with the purpose of imparting additional functionalities and enhancing the matrix-fibre interaction. It is found that both carbon fibres and modified graphene significantly influence the crystallization behaviour and smaller, and/or more imperfect crystals appear while the degree of crystallinity decreases. Despite this, nanoindentation studies show that the PEEK layer exhibits significant modulus improvements (≈30%) for 5 wt.% of graphene. Most importantly, the study of the local mechanical properties by nanoindentation mapping allows the identification of remarkably high modulus values close to the carbon fibre front. Such a relevant mechanical enhancement can be associated with the accumulation of graphene platelets at the polymer-fibre boundary, as revealed by electron microscopy studies. The results offer a feasible route for interlaminar mechanical improvement based on the higher density of graphene platelets at the fibre front that should promote interfacial interactions. Concerning electrical conductivity, a large anisotropy was found for all laminates, and values in the range ~10-4 S/cm were found for the through-thickness arrangement as a consequence of the good consolidation of the laminates.

Graphene and Polyethylene: A Strong Combination Towards Multifunctional Nanocomposites.

The key to the preparation of polymer nanocomposites with new or improved properties resides in the homogeneous dispersion of the filler and in the efficient load transfer between components through strong filler/polymer interfacial interactions. This paper reports on the preparation of a series of nanocomposites of graphene and a polyolefin using different experimental approaches, with the final goal of obtaining multifunctional materials. A high-density polyethylene (HDPE) is employed as the matrix, while unmodified and chemically modified graphene fillers are used. By selecting the correct combination as well as the adequate preparation process, the nanocomposites display optimized thermal and mechanical properties, while also conferring good gas barrier properties and significant levels of electrical conductivity.

Photothermally enhanced bactericidal activity by the combined effect of NIR laser and unmodified graphene oxide against Pseudomonas aeruginosa.

The manuscript shows the application of unmodified graphene oxide (GO) as a photothermally susceptible material to trigger antibacterial effects. The synthesis and characterization of unmodified GO easily dispersed in aqueous solutions is also shown. High GO concentrations in the dark and low GO concentrations irradiated with near infrared light (NIR) produced death in nosocomial bacterium (Pseudomonas aeruginosa). It is demonstrated that GO dispersion in the dark produced a dose-dependent increase in the antibacterial action at concentrations up to 120 µg/mL. On the other hand, by using much lower concentrations (c.a. 2 µg/mL) of GO (non toxic in the dark) and irradiating with near-infrared radiation during 15 min, a degree of mortality of 98.49% was observed. The P. aeruginosa treated with GO and irradiated exhibited DNA fragmentation due to the physical damage of cell membranes. The GO 2 µg/mL dispersions proved favorable, since they do not induce cell death in the dark, whereas the combination with NIR light triggers the damage to the cell membranes. This characteristic is clearly an advantage in comparison with traditional antibacterial nanomaterials (such as nanoparticles), which induce cell killing due to the nanoparticles toxicity per se. Furthermore, this work provides a novel treatment for combating bacterial nosocomial infections without the use of antibiotics, opening a new area of clinical application via simple photothermal therapy.

Chemistry below graphene: decoupling epitaxial graphene from metals by potential-controlled electrochemical oxidation.

While high-quality defect-free epitaxial graphene can be efficiently grown on metal substrates, strong interaction with the supporting metal quenches its outstanding properties. Thus, protocols to transfer graphene to insulating substrates are obligatory, and these often severely impair graphene properties by the introduction of structural or chemical defects. Here we describe a simple and easily scalable general methodology to structurally and electronically decouple epitaxial graphene from Pt(111) and Ir(111) metal surfaces. A multi-technique characterization combined with ab-initio calculations was employed to fully explain the different steps involved in the process. It was shown that, after a controlled electrochemical oxidation process, a single-atom thick metal-hydroxide layer intercalates below graphene, decoupling it from the metal substrate. This decoupling process occurs without disrupting the morphology and electronic properties of graphene. The results suggest that suitably optimized electrochemical treatments may provide effective alternatives to current transfer protocols for graphene and other 2D materials on diverse metal surfaces.

Facile one-pot exfoliation and integration of 2D layered materials by dispersion in a photocurable polymer precursor.

Efficient exfoliation of graphene and related materials (GRM) and fast and inexpensive integration/assembly are crucial to fulfil their full potential. A high degree of exfoliation in organic media can be achieved with high boiling point liquids that usually leave residues after drying, which is a handicap for many applications. Here, the effective exfoliation and dispersion of GRM in a vinyl monomer, which is subsequently converted to a functional polymer by photopolymerization, is reported. Nanocomposite membranes and three-dimensional objects are produced by the photo-curing process and stereolithography 3D printing, respectively.

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst.

Polyaniline is a conductive polymer with distinctive optical and electrical properties. Its enzymatic synthesis is an environmentally friendly alternative to the use of harsh oxidants and extremely acidic conditions. 7D5L, a high-redox potential laccase developed in our lab, is the biocatalyst of choice for the synthesis of green polyaniline (emeraldine salt) due to its superior ability to oxidize aniline and kinetic stability at the required polymerization conditions (pH 3 and presence of anionic surfactants) as compared with other fungal laccases. Doses as low as 7.6 nM of 7D5L catalyze the polymerization of 15 mM aniline (in 24 h, room temperature, 7% yield) in the presence of different anionic surfactants used as doping templates to provide linear and water-soluble polymers. Aniline polymerization was monitored by the increase of the polaron absorption band at 800 nm (typical for emeraldine salt). Best polymerization results were obtained with 5 mM sodium dodecylbenzenesulfonate (SDBS) as template. At fixed conditions (15 mM aniline and 5mM SDBS), polymerization rates obtained with 7D5L were 2.5-fold the rates obtained with commercial Trametes villosa laccase. Moreover, polyaniline yield was notably boosted to 75% by rising 7D5L amount to 0.15 µM, obtaining 1g of green polyaniline in 1L-reaction volume. The green polymer obtained with the selected system (7D5L/SDBS) holds excellent electrochemical and electro-conductive properties displayed in water-dispersible nanofibers, which is advantageous for the nanomaterial to be readily cast into uniform films for different applications.

Influence of the covalent immobilization of graphene oxide in poly(vinyl alcohol) on human osteoblast response.

The differences in the response of human Saos-2 osteoblasts to nanocomposites of poly(vinyl alcohol) (PVA) and 1.5wt.% graphene oxide (GO) prepared by covalent linking (PVA/GO-c) and simple blending (PVA/GO-m) have been evaluated through different biocompatibility parameters. The effects produced on osteoblasts by these two nanocomposites were analysed in parallel and compared with the direct action of GO and with the effect of PVA films without GO. The intracellular content of reactive oxygen species (ROS) and the levels of interleukin-6 (IL-6) were measured to evaluate oxidative stress induction and protective response, respectively. The results demonstrate that the combination of GO with PVA reduces both the proliferation delay and the internal cell complexity alterations induced by GO on human osteoblasts. Moreover, the covalent attachment of GO to the PVA chains increases both cell viability and IL-6 levels, reducing both apoptosis and intracellular ROS content when compared to simple blending of both materials. The use of this strategy to modulate the biointerface reduces the toxic effects of graphene while preserving the reinforcement characteristics for application in tissue engineering scaffolds, and has enormous interest for polymer/graphene biomaterials development.

Comparative study of the covalent diazotization of graphene and carbon nanotubes using thermogravimetric and spectroscopic techniques.

The direct diazotization of the sp(2) carbon network of graphene and multi-walled carbon nanotubes (MWNTs) is one of the many methods employed to introduce functional groups into these nanostructures. Herein, a methodical study on solvent-free diazotization with ethynylaniline in the presence of isoamyl nitrite is reported. Thermogravimetric analysis and UV-visible, infrared and Raman spectroscopies are used to precisely determine the degree of modification, confirm the presence of physisorption and describe the mechanism of elimination of the modifying groups. The results suggest that the same synthetic protocol in both cases leads to a certain degree of covalent modification, whilst a proportion of the modifying groups remains adsorbed to the carbon nanostructure. A higher level of global modification was observed for MWNTs. It was found that the elimination mechanism of the covalently-linked modifiers is identical for both nanostructures and involves two steps; acetylenic-aromatic bond rupture in the modifier followed by modifier-carbon nanostructure cleavage.

A versatile chemical tool for the preparation of conductive graphene-based polymer nanocomposites.

A general route for the functionalization of graphene and graphene derivatives with a low molecular weight polymer by thiol-radical reactions is reported. Polymer-modified graphene is employed as a filler for high density polyethylene to generate materials with good electrical conductivity.

"Click"-functionalization of [60]fullerene and graphene with an unsymmetrically functionalized diketopyrrolopyrrole (DPP) derivative.

A synthetic strategy is developed that allows for the facile functionalization of carbon nanostructures thus providing the possibility of comparing the striking different optical and electrochemical properties of ensembles based on the diketopyrrolopyrrole (DPP) chromophore covalently attached to either [60]fullerene or graphene.

Graphene functionalisation with a conjugated poly(fluorene) by click coupling: striking electronic properties in solution.

Graphene flakes covalently modified with a conjugated polymer, poly[(9,9-dihexylfluorene)-co-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFA), were efficiently synthesised by a Cu-catalysed Huisgen 1,3-dipolar cycloaddition between alkyne-modified graphene and an azide-functionalised polymer. Two approaches for the modification of graphene with alkyne groups were investigated (coupling with a diazonium salt generated in situ or an amidation reaction) and the optimum conditions determined. The success of the click-coupling approach was confirmed by FTIR, (1)H NMR, Raman, and X-ray photoelectron spectroscopy (XPS). The absorption and emission spectra of the click product show a strong solvent dependency.

Recent advances in the covalent modification of graphene with polymers.

Covalent binding of polymers to graphene represents an interesting alternative for the development of novel composite materials with a compendium of interfacial interactions. Through covalent linking, the concept of interface changes from a traditional view of interactions between components, such as van der Waals, hydrogen bonding, and so on, that is to say, at a polymer-filler interface, to a single compound concept where graphene forms an integral part of the polymeric chains. This feature article provides an overview of the strategies currently employed to functionalize graphene with polymers. We focus on the grafting-from and grafting-to methods used to bind polymers to graphene. The advantages and drawbacks, as well as the influence of each method on the final properties, are highlighted.

Supramolecular assembly of graphene with functionalized poly(fluorene-alt-phenylene): the role of the anthraquinone pendant groups.

Hybrid materials composed of graphene and conjugated poly(fluorene-alt-phenylene) endowed with redox-active anthraquinone moieties are prepared. Remarkable changes in the electronic properties of the polymer are observed. Effective interactions among the pendant anthraquinone and graphene, likely due to π-π stacking, are confirmed.

Easy way to fabricate nanostructures on a reactive polymer surface.

The fabrication of advanced architectures in poly(glycidylmethacrylate-co-styrene) (PGMA-S) copolymers using direct laser interference patterning (DLIP) and its selective functionalization is reported. The structure features depend mainly on the laser energy used and on the styrene content in the copolymer. The topography, measured by electronic scanning microscopy, show regular and ordered arrays for the polystyrene (PS) and for the copolymers PGMA-S. The surface PS homopolymer is ablated at the position of maximum light fluence (constructive interference), while in the copolymers the surfaces swell up at the regions with maximal fluence. The styrene units are shown to absorb the laser energy giving photothermally ablated regions or promoting the chemical decomposition of acrylate units or polymer segments. In that way, DLIP provides a unique way to produce regularly ordered structures protruding or depressing from the polymer surface without altering to a large extent the chemical nature of the material. In addition, it is shown, using fluorescence microscopy, that amine-polyethylenglycol-CdSe quantum dots (NH(2)-PEG-QDs) could be spatially localized by reaction with patterned surfaces of PGMA-S. In that way, it is proven that a patterned and chemically reactive surface can be created using DLIP of PGMA-S.

Fabrication of highly ordered arrays of platinum nanoparticles using direct laser interference patterning.

Highly ordered electrode arrays composed of lines of platinum nanoparticles deposited onto gold substrates have been made by direct laser interference patterning of polyaniline thin films, followed by electrochemical deposition of platinum nanoparticles. Nanostructured arrays of electrocatalytic platinum particles are built in that way.

Chemical lithography of a conductive polymer using a traceless removable group.

Polyaniline could be easily converted into nitrosated polyaniline by reaction with nitrite ion in acids. The product is soluble in common solvents and could be deposited into thin films. The nitrosated polyaniline could be back-converted into polyaniline by acid hydrolysis. On the basis of those properties, a simple chemical lithographic process to produce conductive polyaniline images is demonstrated.