On the design of lignin reinforced acrylic acid/hyaluronic acid adhesive hydrogels with conductive PEDOT:HA nanoparticles.

Hydrogels are of great importance in biomedical engineering. They possess the ability to mimic bodily soft tissues, and this allows exciting possibilities for applications such as tissue engineering, drug delivery and wound healing, however much work remains on stability and mechanical robustness to allow for translation to clinical applications. The work herein describes the synthesis and analysis of a biocompatible, versatile hydrogel that has tailorable swelling, high stability when swollen and thermal stability. The synthesis methods used produce a hydrogel with high elasticity, good mechanical properties and rapid crosslinking whilst displaying biocompatibility, adhesion, and conductivity. It has been shown that cell viability in the samples is above 80 % in all cases, a Young's Modulus of up to 85 kPa and high swelling degrees were achieved. These materials show potential for use in numerous applications such as adhesive sensors, skin grafts and drug delivery systems.

Coating of Felt Fibers with Carbon Nanotubes and PEDOT with Different Counterions: Temperature and Electrical Field Effects.

The use of wearable devices has promoted new ways of integrating these devices, one of which is through the development of smart textiles. Smart textiles must possess the mechanical and electrical properties necessary for their functionality. This study explores the impact of polymer-felt microstructure variations on their morphology, electrical, and mechanical properties. The application of thermal treatment, along with an electric field, leads to a substantial structural reorganization of the molecular chains within pristine felt. This results in a system of nanofibrils coated with MWCNT-PEDOT, characterized by highly ordered counterions that facilitate the flow of charge carriers. Both temperature and an electric field induce reversible microstructural changes in pristine felt and irreversible changes in coated felt samples. Furthermore, electropolymerization of PEDOT significantly enhances electrical conductivity, with PEDOT:BTFMSI-coated fabric exhibiting the highest conductivity.

Electroconductive PEDOT nanoparticle integrated scaffolds for spinal cord tissue repair.

BACKGROUND: Hostile environment around the lesion site following spinal cord injury (SCI) prevents the re-establishment of neuronal tracks, thus significantly limiting the regenerative capability. Electroconductive scaffolds are emerging as a promising option for SCI repair, though currently available conductive polymers such as polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) present poor biofunctionality and biocompatibility, thus limiting their effective use in SCI tissue engineering (TE) treatment strategies. METHODS: PEDOT NPs were synthesized via chemical oxidation polymerization in miniemulsion. The conductive PEDOT NPs were incorporated with gelatin and hyaluronic acid (HA) to create gel:HA:PEDOT-NPs scaffolds. Morphological analysis of both PEDOT NPs and scaffolds was conducted via SEM. Further characterisation included dielectric constant and permittivity variances mapped against morphological changes after crosslinking, Young's modulus, FTIR, DLS, swelling studies, rheology, in-vitro, and in-vivo biocompatibility studies were also conducted. RESULTS: Incorporation of PEDOT NPs increased the conductivity of scaffolds to 8.3 × 10-4 ± 8.1 × 10-5 S/cm. The compressive modulus of the scaffold was tailored to match the native spinal cord at 1.2 ± 0.2 MPa, along with controlled porosity. Rheological studies of the hydrogel showed excellent 3D shear-thinning printing capabilities and shape fidelity post-printing. In-vitro studies showed the scaffolds are cytocompatible and an in-vivo assessment in a rat SCI lesion model shows glial fibrillary acidic protein (GFAP) upregulation not directly in contact with the lesion/implantation site, with diminished astrocyte reactivity. Decreased levels of macrophage and microglia reactivity at the implant site is also observed. This positively influences the re-establishment of signals and initiation of healing mechanisms. Observation of axon migration towards the scaffold can be attributed to immunomodulatory properties of HA in the scaffold caused by a controlled inflammatory response. HA limits astrocyte activation through its CD44 receptors and therefore limits scar formation. This allows for a superior axonal migration and growth towards the targeted implantation site through the provision of a stimulating microenvironment for regeneration. CONCLUSIONS: Based on these results, the incorporation of PEDOT NPs into Gel:HA biomaterial scaffolds enhances not only the conductive capabilities of the material, but also the provision of a healing environment around lesions in SCI. Hence, gel:HA:PEDOT-NPs scaffolds are a promising TE option for stimulating regeneration for SCI.

Effect of Chitin Whiskers on the Molecular Dynamics of Carrageenan-Based Nanocomposites.

Films of carrageenan (KC) and glycerol (g) with different contents of chitin nanowhiskers (CHW) were prepared by a solution casting process. The molecular dynamics of pure carrageenan (KC), carrageenan/glycerol (KCg) and KCg with different quantities of CHWs as a filler was studied using dielectric relaxation spectroscopy. The analysis of the CHW effect on the molecular mobility at the glass transition, Tg, indicates that non-attractive intermolecular interactions between KCg and CHW occur. The fragility index increased upon CHW incorporation, due to a reduction in the polymer chains mobility produced by the CHW confinement of the KCg network. The apparent activation energy associated with the relaxation dynamics of the chains at Tg slightly increased with the CHW content. The filler nature effect, CHW or montmorillonite (MMT), on the dynamic mobility of the composites was analyzed by comparing the dynamic behavior of both carrageenan-based composites (KCg/xCHW, KCg/xMMT).

Molecular Dynamics of Functional Azide-Containing Acrylic Films.

A report on the syntheses, thermal, mechanical and dielectric characterizations of two novel polymeric acrylic materials with azide groups in their pendant structures is presented. Having the same general structure, these polymers differ in length of oxyethylene units in the pendant chain [-CONH-CH2CH2-(O-CH2CH2)nN3], where n is 1 (poly(N-(2-(2-azidoethoxy)ethyl)methacrylamide), PAzMa1) or 2 (poly(N-2-(2-(2-azidoethoxy)ethoxy)ethyl)methacrylamide), PAzMa2), leading with changes in their dynamics. As the thermal decomposition of the azide group is observed above 100 °C, dielectric analysis was carried out in the temperature range of -120 °C to 100 °C. Dielectric spectra of both polymers exhibit in the glassy state two relaxations labelled in increasing order of temperature as γ- and ß-processes, respectively. At high temperatures and low frequencies, the spectra are dominated by ohmic conductivity and interfacial polarization effects. Both, dipolar and conductive processes were characterized by using different models. Comparison of the dielectric activity obtained for PAzMa1 and PAzMa2 with those reported for crosslinked poly(2-ethoxyethylmethacrylate) (CEOEMA) was performed. The analysis of the length of oxyethylene pendant chain and the effect of the methacrylate or methacrylamide nature on the dynamic mobility was analysed.

The effect of cross-linking on the molecular dynamics of the segmental and ß Johari-Goldstein processes in polyvinylpyrrolidone-based copolymers.

The effect of the cross-link density on the molecular dynamics of copolymers composed of vinylpyrrolidone (VP) and butyl acrylate (BA) was studied using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). A single glass transition was detected by DSC measurements. The dielectric spectra exhibit conductive processes and three dipolar relaxations labeled as α, ß and γ in the decreasing order of temperatures. The cross-linker content affects both α and ß processes, but the fastest γ process is relatively unaffected. An increase of cross-linking produces a typical effect on the α process dynamics: (i) the glass transition temperature is increased, (ii) the dispersion is broadened, (iii) its strength is decreased and (iv) the relaxation times are increased. However, the ß process, which possesses typical features of a pure Johari-Goldstein relaxation, unexpectedly loses the intermolecular character for the highest cross-linker content.