RESUMO
Hydrogels are a popular class of biomaterial that are used in a number of commercial applications (e.g.; contact lenses, drug delivery, and prophylactics). Alginate-based tough hydrogel systems, interpenetrated with acrylamide, reportedly form both ionic and covalent cross-links, giving rise to their remarkable mechanical properties. In this work, we explore the nature, onset and extent of such hybrid bonding interactions between the complementary networks in a model double-network alginate-acrylamide system, using a host of characterisation techniques (e.g.; FTIR, Raman, UV-vis, and fluorescence spectroscopies), in a time-resolved manner. Further, due to the similarity of bonding effects across many such complementary, interpenetrating hydrogel networks, the broad bonding interactions and mechanisms observed during gelation in this model system, are thought to be commonly replicated across alginate-based and broader double-network hydrogels, where both physical and chemical bonding effects are present. Analytical techniques followed real-time bond formation, environmental changes and re-organisational processes that occurred. Experiments broadly identified two phases of reaction; phase I where covalent interaction and physical entanglements predominate, and; phase II where ionic cross-linking effects are dominant. Contrary to past reports, ionic cross-linking occurred more favourably via mannuronate blocks of the alginate chain, initially. Evolution of such bonding interactions was also correlated with the developing tensile and compressive properties. These structure-property findings provide mechanistic insights and future synthetic intervention routes to manipulate the chemo-physico-mechanical properties of dynamically-forming tough hydrogel structures according to need (i.e.; durability, biocompatibility, adhesion, etc.), allowing expansion to a broader range of more physically and/or environmentally demanding biomaterials applications.
RESUMO
Silver nanoparticle (AgNP) and AgNP/reduced graphene oxide (rGO) nanocomposite impregnated medical grade polyviscose textile pads were formed using a facile, surface-mediated wet chemical solution-dipping process, without further annealing. Surfaces were sequentially treated in situ with a sodium borohydride (NaBH4) reducing agent, prior to formation, deposition, and fixation of Ag nanostructures and/or rGO nanosheets throughout porous non-woven (i.e., randomly interwoven) fibrous scaffolds. There was no need for stabilising agent use. The surface morphology of the treated fabrics and the reaction mechanism were characterised by Fourier transform infrared (FTIR) spectra, ultraviolet-visible (UV-Vis) absorption spectra, X-ray diffraction (XRD), Raman spectroscopy, dynamic light scattering (DLS) energy-dispersive X-ray analysis (EDS), and scanning electron microscopic (SEM). XRD and EDS confirmed the presence of pure-phase metallic silver. Variation of reducing agent concentration allowed control over characteristic plasmon absorption of AgNP while SEM imaging, EDS, and DLS confirmed the presence of and dispersion of Ag particles, with smaller agglomerates existing with concurrent rGO use, which also coincided with enhanced AgNP loading. The composites demonstrated potent antimicrobial activity against the clinically relevant gram-negative Escherichia coli (a key causative bacterial agent of healthcare-associated infections; HAIs). The best antibacterial rate achieved for treated substrates was 100% with only a slight decrease (to 90.1%) after 12 equivalent laundering cycles of standard washing. Investigation of silver ion release behaviours through inductively coupled plasmon optical emission spectroscopy (ICP-OES) and laundering durability tests showed that AgNP adhesion was aided by the presence of the rGO host matrix allowing for robust immobilisation of silver nanostructures with relatively high stability, which offered a rapid, convenient, scalable route to conformal NP-decorated and nanocomposite soft matter coatings.
