RESUMEN
Inspired by spider silk's hierarchical diversity, we leveraged peptide motifs with the capability to tune structural arrangement for controlling the mechanical properties of a conventional polymer framework. The addition of nanofiller with hydrogen bonding sites was used as another pathway towards hierarchical tuning via matrix-filler interactions. Specifically, peptide-polyurea hybrids (PPUs) were combined with cellulose nanocrystals (CNCs) to develop mechanically-tunable nanocomposites via tailored matrix-filler interactions (or peptide-cellulose interactions). In this material platform, we explored the effect of these matrix-filler interactions on the secondary structure, hierarchical ordering, and mechanical properties of the peptide hybrid nanocomposites. Interactions between the peptide matrix and CNCs occur in all of the PPU/CNC nanocomposites, preventing α-helical ordering, but promoting inter-molecular hydrogen bonded ß-sheet formation. Depending on peptide and CNC content, the Young's modulus varies from 10 to 150 MPa. Unlike conventional cellulose-reinforced polymer nanocomposites, the mechanical properties of these composite materials are dictated by a balance of CNC reinforcement, peptidic ordering, and microphase-separated morphology. This research highlights that leveraging peptide-cellulose interactions is a strategy to create materials with targeted mechanical properties for a specific application using a limited selection of building blocks.
Asunto(s)
Celulosa , Nanocompuestos , Celulosa/química , Polímeros/química , Péptidos , Módulo de Elasticidad , Nanocompuestos/químicaRESUMEN
The reinforcement of polymer nanocomposites can be achieved through alignment or percolation of cellulose nanocrystals (CNCs). Here, we compare the efficacy of these reinforcement mechanisms in thermoplastic polyurethane (PU) elastomer nanocomposites containing thermally stable cotton CNCs. CNC alignment was achieved by melt spinning nanocomposite fibers, while a percolating CNC network was generated by solvent casting nanocomposite films with CNC contents up to 20 wt %. While in films both the CNCs and the PU matrix were entirely isotropic at all concentrations as confirmed by wide-angle X-ray scattering and birefringence analysis, the CNCs in the fibers exhibited a preferential orientation, which improved with increasing CNC concentration. Increasing the CNC concentration in the fibers reduces, however, the alignment of the PU chains, resulting in an entirely isotropic PU matrix at high CNC contents. The mechanical properties of films and fibers were evaluated using stress-strain measurements. Nanocomposite fibers with low CNC content exhibited superior stiffness, extensibility, and strength compared to the films, while the films displayed superior mechanical properties at high CNC concentrations. These findings are rationalized using common semiempirical models describing the reinforcing effects of CNC alignment in fibers (Halpin-Tsai) and CNC percolation in films (percolation model). The formation of a percolating CNC network leads to a stronger reinforcement than CNC alignment, as the reinforcing effect of the latter is limited by the comparably low aspect ratio of CNCs extracted from cotton. As a consequence, above the percolation threshold for cotton CNCs, isotropic nanocomposite PU films show a higher stiffness than aligned nanocomposite PU fibers.
RESUMEN
Inspired by Nature's tunability driven by the modulation of structural organization, we utilize peptide motifs as an approach to tailor not only hierarchical structure, but also thermo-responsive shape memory properties of conventional polymeric materials. Specifically, poly(ß-benzyl-L-aspartate)-b-poly(dimethylsiloxane)-b-poly(ß-benzyl-L-aspartate) was incorporated as the soft segment in peptide-polyurea hybrids to manipulate hierarchical ordering through peptide secondary structure and a balance of inter- and intra-molecular hydrogen bonding. Employing these bioinspired peptidic polyureas, we investigated the influence of secondary structure on microphase-separated morphology, and shape fixity and recovery via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), small-angle X-ray scattering (SAXS) and dynamic mechanical analysis (DMA). The ß-sheet motifs promoted phase mixing through extensive inter-molecular hydrogen bonding between the hard block and peptide segments and provided an increased chain elasticity, resulting in decreased shape fixity compared to a non-peptidic control. In contrast, intra-molecular hydrogen bonding driven by the α-helical arrangements yielded a microphase-separated and hierarchically ordered morphology, leading to an increase in the shape fixing ratio. These results indicate that peptide secondary structure provides a convenient handle for tuning shape memory properties by regulating hydrogen bonding with the surrounding polyurea hard segment, wherein extent of hydrogen bonding and phase mixing between the peptidic block and hard segment dictate the resulting shape memory behaviour. Furthermore, the ability to shift secondary structure as a function of temperature was also demonstrated as a pathway to influence shape memory response. This research highlights that peptide secondary conformation influences the hierarchical ordering and modulates the shape memory response of peptide-polymer hybrids. We anticipate that these findings will enable the design of smart bio-inspired materials with responsive and tailored function via a balance of hydrogen bonding character, structural organization, and mechanics.
RESUMEN
Tunicate cellulose nanofibers (CNFs) have received widespread attention as renewable and eco-friendly engineering materials because of their high crystallinity and mechanical stiffness. Here, we report the effects of disintegration process conditions on structure-property relationships of tunicate CNFs. By varying the hydrolysis time, we could establish a correlation between crystallinity of the CNFs with linearity and stiffness, which produces different molecular ordering within their nanostructured films. Despite having identical raw materials, tensile strength and thermal conductivity of the resulting layered films varied widely, ranging from 95.6 to 205 MPa and from 1.08 to 2.37 W/mK respectively. Furthermore, nanolayered CNF films provided highly anisotropic thermal conductivities with an in- and through-plane ratio of 21.5. Our systematic investigations will provide general and practical strategies in tailoring material properties for emerging engineering applications, including flexible paper electronics, heat sink adhesives and biodegradable, implantable devices.
Asunto(s)
Materiales Biocompatibles/química , Celulosa/química , Nanocompuestos/química , Nanofibras/química , Urocordados/química , Animales , Cristalización , Hidrólisis , Membranas Artificiales , Nanocompuestos/ultraestructura , Nanofibras/ultraestructura , Resistencia a la Tracción , Urocordados/fisiologíaRESUMEN
We report the electrospinning of mechanically-tunable, cellulose nanocrystal (CNC)-reinforced polyurethanes (PUs). Using high-aspect ratio CNCs from tunicates, the stiffness and strength of electrospun PU/CNC mats are shown to generally increase. Furthermore, by tuning the electrospinning conditions, fibrous PU/CNC mats were created with either aligned or non-aligned fibers, as confirmed by scanning electron microscopy. PU/CNC mats having fibers aligned in the strain direction were stiffer and stronger compared to mats containing non-aligned fibers. Interestingly, fiber alignment was accompanied by an anisotropic orientation of the CNCs, as confirmed by wide-angle X-ray scattering, implying their alignment additionally benefits both stiffness and strength of fibrous PU/CNC nanocomposite mats. These findings suggest that CNC alignment could serve as an additional reinforcement mechanism in the design of stronger fibrous nanocomposite mats.
RESUMEN
Natural melanins are biocompatible conductors with versatile functionalities. Here, we report fabrication of multifunctional poly(vinyl alcohol)/melanin nanocomposites by layer-by-layer (LBL) assembly using melanin nanoparticles (MNPs) directly extracted from sepia officinalis inks. The LBL assembly offers facile manipulation of nanotextures as well as nm-thickness control of the macroscale film by varying solvent qualities. The time-resolved absorption was monitored during the process and quantitatively studied by fractal dimension and lacunarity analysis. The capability of nanoarchitecturing provides confirmation of complete monolayer formation and leads to tunable iridescent reflective colors of the MNP films. In addition, the MNP films have durable electrochemical conductivities as evidenced by enhanced charge storage capacities for 1000 cycles. Moreover, the MNP covered ITO (indium tin oxide) substrates significantly reduced secretion of inflammatory cytokines, TNF-α, by raw 264.7 macrophage cells compared to bare ITO, by a factor of 5 and 1.8 with and without lipopolysaccharide endotoxins, respectively. These results highlight the optoelectronic device-level tunability along with the anti-inflammatory biocompatibility of the MNP LBL film. This combination of performance should make these films particularly interesting for bioelectronic device applications such as electroceuticals, artificial bionic organs, biosensors, and implantable devices.