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    Mechanically reinforced catechol-containing hydrogels with improved tissue gluing performance
    (Basel : MDPI, 2017) Feng, Jun; Ton, Xuan-Anh; Zhao, Shifang; Paez, Julieta I.; del Campo, Aránzazu
    In situ forming hydrogels with catechol groups as tissue reactive functionalities are interesting bioinspired materials for tissue adhesion. Poly(ethylene glycol) (PEG)–catechol tissue glues have been intensively investigated for this purpose. Different cross-linking mechanisms (oxidative or metal complexation) and cross-linking conditions (pH, oxidant concentration, etc.) have been studied in order to optimize the curing kinetics and final cross-linking degree of the system. However, reported systems still show limited mechanical stability, as expected from a PEG network, and this fact limits their potential application to load bearing tissues. Here, we describe mechanically reinforced PEG–catechol adhesives showing excellent and tunable cohesive properties and adhesive performance to tissue in the presence of blood. We used collagen/PEG mixtures, eventually filled with hydroxyapatite nanoparticles. The composite hydrogels show far better mechanical performance than the individual components. It is noteworthy that the adhesion strength measured on skin covered with blood was >40 kPa, largely surpassing (>6 fold) the performance of cyanoacrylate, fibrin, and PEG–catechol systems. Moreover, the mechanical and interfacial properties could be easily tuned by slight changes in the composition of the glue to adapt them to the particular properties of the tissue. The reported adhesive compositions can tune and improve cohesive and adhesive properties of PEG–catechol-based tissue glues for load-bearing surgery applications.
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    Ferric Ions Crosslinked Epoxidized Natural Rubber Filled with Carbon Nanotubes and Conductive Carbon Black Hybrid Fillers
    (Basel : MDPI, 2022-10-18) Damampai, Kriengsak; Pichaiyut, Skulrat; Stöckelhuber, Klaus Werner; Das, Amit; Nakason, Charoen
    Natural rubber with 50 mol % epoxidation (ENR-50) was filled with carbon nanotubes (CNTs) and conductive carbon black (CCB) hybrid fillers with various CCB loadings of 2.5, 5.0, 7.0, 10.0 and 15.0 phr, and the compounds were mixed with ferric ion (Fe3+) as a crosslinking agent. The ENRs filled exclusively with CNTs, and CNT–CCB hybrid fillers exhibited typical curing curves at different CCB loadings, i.e., increasing torque with time and thus crosslinked networks. Furthermore, the incorporation of CNT–CCB hybrid fillers and increasing CCB loadings caused an enhancement of tensile properties (modulus and tensile strength) and crosslink densities, which are indicated by the increasing torque difference and the crosslink densities. The crosslink densities are determined by swelling and temperature scanning stress relaxation (TSSR). Increasing CCB loadings also caused a significant improvement in bound rubber content, filler–rubber interactions, thermal resistance, glass transition temperature (Tg) and electrical conductivity. A combination of 7 phr CNT and CCB with loading higher than 2.5 phr gave superior properties to ENR vulcanizates. Furthermore, the secondary CCB filler contributes to the improvement of CNT dispersion in the ENR matrix by networking the CNT capsules and forming CNT–CCB–CNT pathways and thus strong CNT–CCB networks, indicating the improvement in the tensile properties, bound rubber content and dynamic properties of the ENR composites. Moreover, higher electrical conductivity with a comparatively low percolation threshold of the hybrid composites was found as compared to the ENR filled with CNTs without CCB composite. The superior mechanical and other properties are due to the finer dispersion and even distribution of CNT–CCB hybrid fillers in the ENR matrix.