Combined Thermomechanical Effect of Graphene Oxide and Montmorillonite on Biobased Epoxy Network Formation for Coatings.

Epoxy nanocomposites derived from linseed oil, reinforced with graphene oxide (GO) and montmorillonite (MMT) nanostructures, were synthesized. The nanohybrids were developed by enriching the structure of MMT and GO with primary amines through a common and simplified method, which implies physical interactions promoted by ultrasonic processing energy. The influence of the new nanoreinforcing agents along with neat ones on the overall properties of the biobased epoxy materials for coating applications was assessed. Interface formation through surface compatibility was contained by the lower values of activation energy calculated from differential scanning calorimetry (DSC) curves, along with a consistent 70% increase in the cross-linking density when amine-modified MMT was used. Thermomechanical characteristics of the biobased epoxy nanocomposites were explained through the interaction of the functional groups over the curing process of epoxidized linseed oil (ELO), giving a 15 °C higher Tg value increase. Furthermore, the low surface energy values suggested an intrinsic antibacterial activity, as proved by a significant decrease of CFU against Staphylococcus aureus bacterial strains on the 0.25% reinforced coatings.

Label-Free DNA Biosensor Based on Reduced Graphene Oxide and Gold Nanoparticles.

Currently available DNA detection techniques frequently require compromises between simplicity, speed, accuracy, and cost. Here, we propose a simple, label-free, and cost-effective DNA detection platform developed at screen-printed carbon electrodes (SPCEs) modified with reduced graphene oxide (RGO) and gold nanoparticles (AuNPs). The preparation of the detection platform involved a two-step electrochemical procedure based on GO reduction onto SPCEs followed by the electrochemical reduction of HAuCl4 to facilitate the post-grafting reaction with AuNPs. The final sensor was fabricated by the simple physical adsorption of a single-stranded DNA (ssDNA) probe onto a AuNPs-RGO/SPCE electrode. Each preparation step was confirmed by morphological and structural characterization using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy, respectively. Furthermore, the electrochemical properties of the modified electrodes have been investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results demonstrated that the introduction of AuNPs onto RGO/SPCEs led to an enhancement in surface conductivity, a characteristic that favored an increased sensitivity in detection. The detection process relied on the change in the electrochemical signal induced by the binding of target DNA to the bioreceptor and was particularly monitored by the change in the charge transfer resistance of a [Fe(CN)6]4-/3- redox couple added in the test solution.

Contribution of the Surface Treatment of Nanofibrillated Cellulose on the Properties of Bio-Based Epoxy Nanocomposites Intended for Flexible Electronics.

The growing interest in materials derived from biomass has generated a multitude of solutions for the development of new sustainable materials with low environmental impact. We report here, for the first time, a strategy to obtain bio-based nanocomposites from epoxidized linseed oil (ELO), itaconic acid (IA), and surface-treated nanofibrillated cellulose (NC). The effect of nanofibrillated cellulose functionalized with silane (NC/S) and then grafted with methacrylic acid (NC/SM) on the properties of the resulted bio-based epoxy systems was thoroughly investigated. The differential scanning calorimetry (DSC) results showed that the addition of NCs did not influence the curing process and had a slight impact on the maximum peak temperature. Moreover, the NCs improved the onset degradation temperature of the epoxy-based nanocomposites by more than 30 °C, regardless of their treatment. The most important effect on the mechanical properties of bio-based epoxy nanocomposites, i.e., an increase in the storage modulus by more than 60% at room temperature was observed in the case of NC/SM addition. Therefore, NC's treatment with silane and methacrylic acid improved the epoxy-nanofiber interface and led to a very good dispersion of the NC/SM in the epoxy network, as observed by the SEM investigation. The dielectric results proved the suitability of the obtained bio-based epoxy/NCs materials as substitutes for petroleum-based thermosets in the fabrication of flexible electronic devices.

Investigating the Synthesis and Characteristics of UV-Cured Bio-Based Epoxy Vegetable Oil-Lignin Composites Mediated by Structure-Directing Agents.

Bio-based composites were developed from the epoxy derivatives of Lallemantia iberica oil and kraft lignin (ELALO and EpLnK), using UV radiation as a low energy consumption tool for the oxiranes reaction. To avoid the filler sedimentation or its inhomogeneous distribution in the oil matrix, different structure-directing agents (SDA) were employed: 1,3:2,4-dibenzylidene-D-sorbitol (DBS), 12-hydroxystearic acid (HSA) and sorbitan monostearate (Span 60). The SDA and EpLnK effect upon the ELALO-based formulations, their curing reaction and the performance of the resulting materials were investigated. Fourier-transform Infrared Spectrometry (FTIR) indicates different modes of molecular arrangement through H bonds for the initial ELALO-SDA or ELALO-SDA-EpLnK systems, also confirming the epoxy group's reaction through the cationic mechanism for the final composites. Gel fraction measurements validate the significant conversion of the epoxides for those materials containing SDAs or 1% EpLnK; an increased EpLnK amount (5%), with or without SDA addition, conduced to an inefficient polymerization process, with the UV radiation being partially absorbed by the filler. Thermo-gravimetric and dynamic-mechanical analyses (TGA and DMA) revealed good properties for the ELALO-based materials. By loading 1% EpLnK, the thermal stability was improved to with 10 °C (for Td3%) and the addition of each SDA differently influenced the Tg values but also gave differences in the glassy and rubbery states when the storage moduli were interrogated, depending on their chemical structures. Water affinity and morphological studies were also carried out.

Control of Dielectric and Mechanical Properties of Styrenic Block Copolymer by Graphite Incorporation.

The structure-property relationship of dielectric elastomers, as well as the methods of improving the control of this relationship, has been widely studied over the last few years, including in some of our previous works. In this paper, we study the control, improvement, and correlation, for a significant range of temperatures, of the mechanical and dielectric properties of polystyrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and maleic-anhydride-grafted SEBS (SEBS-MA) by using graphite (G) as filler in various concentrations. The aim is to analyze the suitability of these composites for converting electrical energy into mechanical energy or vice versa. The dielectric spectroscopy analysis performed in the frequency range of 10 to 1 MHz and at temperatures between 27 and 77 °C emphasized an exponential increase in real permittivity with G concentration, a low level of dielectric losses (≈10-3), as well as the stability of dielectric losses with temperature for high G content. These results correlate well with the increase in mechanical stiffness with an increase in G content for both SEBS/G and SEBS-MA/G composites. The activation energies for the dielectric relaxation processes detected in SEBS/G and SEBS-MA/G composites were also determined and discussed in connection with the mechanical, thermal, and structural properties resulting from thermogravimetric analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses.

Comparative Thermo-Mechanical Properties of Sustainable Epoxy Polymer Networks Derived from Linseed Oil.

Considering its great industrial potential, epoxidized linseed oil (ELO) was crosslinked with different agents, both natural and synthetic: citric acid (CA, in the presence of water-W, or tetrahydrofuran-THF, as activator molecules) and Jeffamine D230, respectively, resulting bio-based polymeric matrices, studied further, comparatively, in terms of their properties, through different methods. Thermal curing parameters were established by means of Differential Scanning Calorimetry (DSC). Fourier transform Infrared Spectroscopy (FTIR) and DSC were used to identify the reactivity of each ELO-based formulation, discussing the influence of the employed curing systems under the conversion of the epoxy rings. Then, the obtained bio-based materials were characterized by different methods, establishing the structure-properties relation. Thermogravimetric analysis revealed higher thermal stability for the ELO_CA material when THF was used as an activator. Moreover, a higher glass transition temperature (Tg) with ~12 °C was registered for this material when compared with the one that resulted through the crosslinking of ELO with D230 conventional amine. Other important features, such as crosslink density, storage modulus, mechanical features, and water affinity, were discussed. Under the loop of a comprehensive approach, a set of remarkable properties were obtained for ELO_CA_THF material when compared with the one resulting from the crosslinking of ELO with the synthetic Jeffamine.

Layered Clay-Graphene Oxide Nanohybrids for the Reinforcement and Fire-Retardant Properties of Polyurea Matrix.

Nanostructures are more and more evolved through extensive research on their functionalities; thus, the aim of this study was to obtain layered clay-graphene oxide nanohybrids with application as reinforcing agents in polyurea nanocomposites with enhanced thermal-mechanical and fire-retardant properties. Montmorillonite (MMT) was combined with graphene oxide (GO) and amine functionalized graphene oxide (GOD) through a new cation exchange method; the complex nanostructures were analyzed through FTIR and XPS to assess ionic interactions between clay layers and GO sheets by C1s deconvolution and specific C sp3, respective/ly, C-O secondary peaks appearance. The thermal decomposition of nanohybrids showed a great influence of MMT layers in TGA, while the XRD patterns highlighted mutual MMT and GO sheets crystalline-structure disruption by the d (002) shift 2θ = 6.29° to lower values. Furthermore, the nanohybrids were embedded in the polyurea matrix, and the thermo-mechanical analysis gave information about the stiffness of MMT-GO nanocomposites, while GOD insertion within the MMT layers resulted in a 30 °C improvement in the Tg of hard domains, as shown in the DSC study. The micro CT analysis show good dispersion of inorganic structures within the polyurea, while the SEM fracture images revealed smooth surfaces. Cone calorimetry was used to evaluate fire-retardant properties through limiting the oxygen index, and MMT-GOD based nanocomposites showed a 35.4% value.

Low Molecular Weight and Polymeric Modifiers as Toughening Agents in Poly(3-Hydroxybutyrate) Films.

The inherent brittleness of poly(3-hydroxybutyrate) (PHB) prevents its use as a substitute of petroleum-based polymers. Low molecular weight plasticizers, such as tributyl 2-acetyl citrate (TAC), cannot properly solve this issue. Herein, PHB films were obtained using a biosynthesized poly(3-hydroxyoctanoate) (PHO) and a commercially available TAC as toughening agents. The use of TAC strongly decreased the PHB thermal stability up to 200 °C due to the loss of low boiling point plasticizer, while minor weight loss was noticed at this temperature for the PHB-PHO blend. Both agents shifted the glass transition temperature of PHB to a lower temperature, the effect being more pronounced for TAC. The elongation at break of PHB increased by 700% after PHO addition and by only 185% in the case of TAC; this demonstrates an important toughening effect of the polymeric modifier. Migration of TAC to the upper surface of the films and no sign of migration in the case of PHO were highlighted by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) results. In vitro biocompatibility tests showed that all the PHB films are non-toxic towards L929 cells and have no proinflammatory immune response. The use of PHO as a toughening agent in PHB represents an attractive solution to its brittleness in the case of packaging and biomedical applications while conserving its biodegradability and biocompatibility.

Poly(3-hydroxybutyrate) Modified by Plasma and TEMPO-Oxidized Celluloses.

Microcrystalline cellulose (MCC) was surface modified by two approaches, namely a plasma treatment in liquid using a Y-shaped tube for oxygen flow (MCC-P) and a TEMPO mediated oxidation (MCC-T). Both treatments led to the surface functionalization of cellulose as illustrated by FTIR and XPS results. However, TEMPO oxidation had a much stronger oxidizing effect, leading to a decrease of the thermal stability of MCC by 80 °C. Plasma and TEMPO modified celluloses were incorporated in a poly(3-hydroxybutyrate) (PHB) matrix and they influenced the morphology, thermal, and mechanical properties of the composites (PHB-MCC-P and PHB-MCC-T) differently. However, both treatments were efficient in improving the fiber-polymer interface and the mechanical properties, with an increase of the storage modulus of composites by 184% for PHB-MCC-P and 167% for PHB-MCC-T at room temperature. The highest increase of the mechanical properties was observed in the composite containing plasma modified cellulose although TEMPO oxidation induced a much stronger surface modification of cellulose. This was due to the adverse effect of more advanced degradation in this last case. The results showed that Y-shaped plasma jet oxidation of cellulose water suspensions is a simple and cheap treatment and a promising method of cellulose functionalization for PHB and other biopolymer reinforcements.

Harnessing a byproduct from wastewater treatment to obtain improved starch/poly(vinyl alcohol) composites.

A rational method to harness a triglyceride-based by-product containing chicken fat traces, extracted from the simulated slaughterhouses wastewater was adopted. Methacrylated linseed oil was used as photo-reactive monomer to "catch" the grease molecules, resulting in a polymeric network (PFrec), further embedded in starch/poly(vinyl alcohol) (St/PVA)-based composites, with or without plasticizer (glycerol-Gly), with enhanced properties. Hydrophobic additive improved the thermal stability of St/PVA blends, an 18 °C increase of Td3 % being registered for PFrec-loaded sample. Mechanical tests revealed that association of PFrec with Gly improved the flexibility and also reinforced the systems, although, no plasticizing effect was observed at PFrec addition. Solubility determinations for the St/PVA-based composite films showed that hydrophobic PFrec increased the water resistance with at least 40 %. According to contact angle measurements a good dispersion of PFrec in the St/PVA network was mediated at the interface by hydrophilic Gly molecules.

Grafting versus Crosslinking of Silk Fibroin-g-PNIPAM via Tyrosine-NIPAM Bridges.

This paper reports the synthesis and complex characterization of novel polymeric networks based on the crosslinking of Bombyx mori silk fibroin via poly(N-isopropylacrylamide) bridges generated by an ammonium cerium nitrate redox system. The research study gives an understanding of the polymerization mechanism in terms of the generation of radical sites, radical growth and termination reaction, as well as the involvement of modifications on silk fibroin structure and properties. The physico-chemical characterization was carried out by FTIR-ATR, X-ray photoelectron spectroscopy and RAMAN spectroscopy with unravelling the chemical modification. The structural characterization and spatial arrangement by secondary structure were carried out by X-ray diffraction and circular dichroism. The thermal behavior and thermal stability were evaluated by differential scanning calorimetry and thermogravimetric analysis. The novel complex polymer network is intended to be used in the field of smart drug delivery systems.

Novel Nanocomposites Based on Functionalized Magnetic Nanoparticles and Polyacrylamide: Preparation and Complex Characterization.

This paper reports the synthesis and complex characterization of nanocomposite hydrogels based on polyacrylamide and functionalized magnetite nanoparticles. Magnetic nanoparticles were functionalized with double bonds by 3-trimethoxysilyl propyl methacrylate. Nanocomposite hydrogels were prepared by radical polymerization of acrylamide monomer and double bond modified magnetite nanoparticles. XPS spectra for magnetite and modified magnetite were recorded to evaluate the covalent bonding of silane modifying agent. Swelling measurements in saline solution were performed to evaluate the behavior of these hydrogels having various compositions. Mechanical properties were evaluated by dynamic rheological analysis for elastic modulus and vibrating sample magnetometry was used to investigate the magnetic properties. Morphology, geometrical evaluation (size and shape) of nanostructural characteristics and the crystalline structure of the samples were investigated by SEM, HR-TEM and selected area electron diffraction (SAED). The nanocomposite hydrogels will be further tested for the soft tissue engineering field as repairing scaffolds, due to their mechanical and magnetization behavior that can stimulate tissue regeneration.

Influence of Graphene Oxide Concentration when Fabricating an Electrochemical Biosensor for DNA Detection.

We have investigated the influence exerted by the concentration of graphene oxide (GO) dispersion as a modifier for screen printed carbon electrodes (SPCEs) on the fabrication of an electrochemical biosensor to detect DNA hybridization. A new pretreatment protocol for SPCEs, involving two successive steps in order to achieve a reproducible deposition of GO, is also proposed. Aqueous GO dispersions of different concentrations (0.05, 0.1, 0.15, and 0.2 mg/mL) were first drop-cast on the SPCE substrates and then electrochemically reduced. The electrochemical properties of the modified electrodes were investigated after each modification step by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), while physicochemical characterization was performed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Finally, the sensing platform was obtained by the simple adsorption of the single-stranded DNA probe onto the electrochemically reduced GO (RGO)-modified SPCEs under optimized conditions. The hybridization was achieved by incubating the functionalized SPCEs with complementary DNA target and detected by measuring the change in the electrochemical response of [Fe(CN)6]3-/4- redox reporter in CV and EIS measurements induced by the release of the newly formed double-stranded DNA from the electrode surface. Our results showed that a higher GO concentration generated a more sensitive response towards DNA detection.

Box-Behnken experimental design for chromium(VI) ions removal by bacterial cellulose-magnetite composites.

In this study bacterial cellulose-magnetite composites were synthesised for the removal of chromium(VI) from aqueous solutions. Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the bacterial cellulose-magnetite composites and to reveal the uniform dispersion of nanomagnetite in the BC matrix. Magnetic properties were also measured to confirm the magnetite immobilization on bacterial cellulose membrane. The effects of initial Cr(VI) concentration, solution pH and solid/liquid ratio upon chromium removal were examined using the statistical Box-Behnken Design. Because of the possibility of magnetite dissolution during chromium(VI) adsorption, the degree of iron leaching was also analysed in the same conditions as Cr(VI) adsorption. From the factors affecting chromium(VI) adsorption the most important was solution pH. The highest Cr(VI) removal efficiency was observed at pH 4, accompanied by the lowest iron leaching in the solution. The adsorption experiments also indicated that the adsorption process of chromium(VI) is well described by Freundlich adsorption model. Our results proved that the BC-magnetite composites could be used for an efficient removal of chromium(VI) from diluted solutions with a minimum magnetite dissolution during operation.