Tissue regeneration requires 3-dimensional (3D) smart materials as scaffolds to promote transport of nutrients. To mimic mechanical properties of extracellular matrices, biocompatible polymers have ...been widely studied and a diverse range of 3D scaffolds have been produced. We propose the use of responsive polymeric materials to create dynamic substrates for cell culture, which goes beyond designing only a physical static 3D scaffold. Here, we demonstrated that lactone- and lactide-based star block-copolymers (SBCs), where a liquid crystal (LC) moiety has been attached as a side-group, can be crosslinked to obtain Liquid Crystal Elastomers (LCEs) with a porous architecture using a salt-leaching method to promote cell infiltration. The obtained SmA LCE-based fully interconnected-porous foams exhibit a Young modulus of 0.23 ± 0.07 MPa and a biodegradability rate of around 20% after 15 weeks both of which are optimized to mimic native environments. We present cell culture results showing growth and proliferation of neurons on the scaffold after four weeks. This research provides a new platform to analyse LCE scaffold-cell interactions where the presence of liquid crystal moieties promotes cell alignment paving the way for a stimulated brain-like tissue.
Natural systems utilize nanofiber architectures to guide water transport, tune mechanical properties, and actuate in response to their environment. In order to harness these properties, a ...hygromorphic bilayer composite comprised of a self-assembled fiber network and an aligned electrospun fiber network was fabricated. Molecular gel self-assembly was utilized to increase hydrophobicity and strength in one layer, while aligned electrospun poly(vinyl alcohol) (PVA) nanofibers increased the rate of hydration and facilitated tunable actuation in the other. Interfacing these two fiber networks in a poly(ethylene oxide-co-epichlorohydrin) (EO-EPI) matrix led to hydration-driven actuation with tunable curvature. Specifically, variations in fiber alignment were achieved by cutting at 0, 90, and 45 degree angles in relation to the length edge of the composite. Along with the ability to program the natural curvature, the utilization of aligned nanofibers increased water transport compared to random nanofiber systems, resulting in a reduction in response time from 20+ minutes to 2-3 minutes.
Nature has achieved diverse functionality via hierarchical organization driven by physical interactions such as hydrogen bonding. Synthetically, polymer-peptide hybrids have been utilized to achieve ...these architectural arrangements and obtain diverse mechanical properties, stimuli responsiveness, and bioactivity. Here, we explore the impact of peptide ordering and soft/hard phase interactions in PEG-based non-chain extended and chain extended peptidic polyurea (PU) and polyurea/polyurethane (PUU) hybrids towards tunable mechanics. Increasing the peptide content of poly(ε-carbobenzyloxy-l-lysine) (PZLY) revealed an increase in α-helical formation and modulation in amine/ether hydrogen bonding, suggesting enhanced intermolecular hydrogen bonding between peptide segments and soft/hard blocks. A balance of phase mixing and microphase segregation was observed depending on competitive hydrogen bonding and the hybrid architecture. This phase behaviour strongly modulated the mechanical response, particularly modulus and extensibility. We anticipate that this solid-state, synthetic framework will expand the reach of our peptide hybrids into biointerfacing materials, including scaffolds and responsive actuators via peptide selection.
A continuous fibrous composite tape of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL) was produced using novel multilayer coextrusion fiber manufacturing. A three-step washing process ...was utilized to remove the PEO matrix, resulting in a PCL fiber mat (>99 wt %). Synchrotron X-ray radiation was utilized to determine the optimized postprocessing uniaxial drawing conditions to achieve efficient crystalline orientation. An examination of small-/wide-angle X-ray scattering (SAXS/WAXS) revealed two regimes in the uniaxial drawing process; at DR < 5, crystalline orientation kinetics were dominant, while at DR > 5, amorphous chain alignment kinetics were dominant. Uniaxial drawing was shown to be an effective tool for tuning individual fiber size from 2.6 ± 0.6 μm by 1.6 ± 0.4 μm in the as-extruded state to 0.31 ± 0.05 μm by 0.13 ± 0.02 μm in the oriented state, while increasing specific surface area 3.5-fold. The elastic modulus and tensile strength of the PCL fiber mat were also increased by a factor of 30 and ∼10, respectively, through uniaxial drawing. Compared to electrospun PCL fiber systems produced with individual fiber dimensions similar to those of the as-extruded and oriented PCL fiber mats, the melt-processed PCL fibers exhibit a 6-fold increase in specific surface area over the corresponding circular, electrospun PCL fibers while maintaining similar thermomechanical properties. The elastic modulus of the oriented, coextruded PCL fiber mat was increased by a factor of 50 compared to the corresponding electrospun PCL fiber mat, while exhibiting a 2.5-fold increase in specific surface area. The ability to melt-process and utilize uniaxial drawing to produce PCL fibers in high volume with a consistent, tunable range of properties that are similar or enhanced when compared to traditional electrospun fibers provides a unique advantage in the field of tissue engineering, surface modification, and drug delivery.
The hierarchical microstructure responsible for the unique energy-absorbing properties of natural materials, like native spider silk and wood, motivated the development of segmented polyurethanes ...with soft segments containing multiple levels of order. As a first step in correlating the effects of crystallinity in the soft segment phase to the hard segment phase, we chose to examine the morphology and mechanical behavior of polyurethanes containing polyether soft blocks with varying tendencies to crystallize and phase segregate and the evolution of the microstructure with deformation. A series of high molecular weight polyurethanes containing poly(ethylene oxide) (PEO) (1000 and 4600
g/mol) and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) (1900
g/mol) soft segments with varying hard segment content were synthesized using a two-step solution polymerization method. The presence of soft segment crystallinity (PEO 1000
g/mol) was shown to improve the storage modulus of the segmented polyurethanes below the
T
m of the soft block and to enhance toughness compared to the PEO–PPO–PEO soft segment polyurethanes. We postulate that this enhancement in mechanical behavior is the result of crystalline soft regions that serve as an additional load-bearing component during deformation. Morphological characterization also revealed that the microstructure of the segmented polyurethanes shifts from soft segment continuous to interconnected and/or hard domain continuous with increasing hard segment size, resulting in diminished ultimate elongation, but enhanced initial moduli and tensile strengths. Tuning the soft segment phase crystallinity may ultimately lead to tougher polyurethane fibers.
One of the key design components of nature is the utilization of hierarchical arrangements to fabricate materials with outstanding mechanical properties. Employing the concept of hierarchy, a new ...class of segmented polyurethane/ureas (PUUs) was synthesized containing either a peptidic, triblock soft segment, or an amorphous, nonpeptidic homoblock block soft segment with either an amorphous or a crystalline hard segment to investigate the effects of bioinspired, multiple levels of organization on thermal and mechanical properties. The peptidic soft segment was composed of poly(benzyl-l-glutamate)-block-poly(dimethylsiloxane)-block-poly(benzyl-l-glutamate) (PBLG-b-PDMS-b-PBLG), restricted to the β-sheet conformation by limiting the peptide segment length to <10 residues, whereas the amorphous soft segment was poly(dimethylsiloxane) (PDMS). The hard segment consisted of either 1,6-hexamethylene diisocyanate (crystalline) or isophorone diisocyanate (amorphous) and chain extended with 1,4-butanediol. Thermal and morphological characterization indicated microphase separation in these hierarchically assembled PUUs; furthermore, inclusion of the peptidic segment significantly increased the average long spacing between domains, whereas the peptide domain retained its β-sheet conformation regardless of the hard segment chemistry. Mechanical analysis revealed an enhanced dynamic modulus for the peptidic polymers over a broader temperature range as compared with the nonpeptidic PUUs as well as an over three-fold increase in tensile modulus. However, the elongation-at-break was dramatically reduced, which was attributed to a shift from a flexible, continuous domain morphology to a rigid, continuous matrix in which the peptide, in conjunction with the hard segment, acts as a stiff reinforcing element.
Natural systems utilize nanofiber architectures to guide water transport, tune mechanical properties, and actuate in response to their environment. In order to harness these properties, a ...hygromorphic bilayer composite comprised of a self-assembled fiber network and an aligned electrospun fiber network was fabricated. Molecular gel self-assembly was utilized to increase hydrophobicity and strength in one layer, while aligned electrospun poly(vinyl alcohol) (PVA) nanofibers increased the rate of hydration and facilitated tunable actuation in the other. Interfacing these two fiber networks in a poly(ethylene oxide-
co
-epichlorohydrin) (EO-EPI) matrix led to hydration-driven actuation with tunable curvature. Specifically, variations in fiber alignment were achieved by cutting at 0, 90, and 45 degree angles in relation to the length edge of the composite. Along with the ability to program the natural curvature, the utilization of aligned nanofibers increased water transport compared to random nanofiber systems, resulting in a reduction in response time from 20+ minutes to 2-3 minutes.
Nanofiber alignment was utilized as a manufacturing strategy for hygromorphic bilayers to control response rate and shape through transport anisotropy.
Poly(vinylidene fluoride-co-tetrafluoroethylene) (PVDF-TFE) is confined between alternating layers of poly(ethylene terephthalate) (PET) utilizing a unique multilayer processing technology, in which ...PVDF-TFE and PET are melt-processed in a continuous fashion. Postprocessing techniques including biaxial orientation and melt recrystallization were used to tune the crystal orientation of the PVDF-TFE layers, as well as achieve crystallinity in the PET layers through strain-induced crystallization and thermal annealing during the melt recrystallization step. A volume additive model was used to extract the effect of crystal orientation within the PVDF-TFE layers and revealed a significant enhancement in the modulus from 730 MPa in the as-extruded state (isotropic) to 840 MPa in the biaxially oriented state (on-edge) to 2230 MPa in the melt-recrystallized state (in-plane). Subsequently, in situ wide-angle X-ray scattering was used to observe the crystal structure evolution during uniaxial deformation in both the as-extruded and melt-recrystallized states. It is observed that the low-temperature ferroelectric PVDF-TFE crystal phase in the as-extruded state exhibits equatorial sharpening of the 110 and 200 crystal peaks during deformation, quantified using the Hermans orientation function, while in the melt-recrystallized state, an overall increase in the crystallinity occurs during deformation. Thus, we correlated the mechanical response (strain hardening) of the films to these respective evolved crystal structures and highlighted the ability to tailor mechanical response. With a better understanding of the structural evolution during deformation, it is possible to more fully characterize the structural response to handling during use of the high-barrier PVDF-TFE/PET multilayer films as commercial dielectrics and packaging materials.
Forced assembly processing provides a unique opportunity to examine the effects of confinement on block copolymers (BCPs) via conventional melt processing techniques. The microlayering process was ...utilized to produce novel materials with enhanced mechanical properties through selective manipulation of layer thickness. Multilayer films consisting of an elastomeric, symmetric block copolymer confined between rigid polystyrene (PS) layers were produced with layer thicknesses ranging from 100 to 600 nm. Deformation studies of the confined BCP showed an increase in ductility as the layer thickness decreased to 190 nm due to a shift in the mode of deformation from crazing to shear yielding. Postextrusion annealing was performed on the multilayer films to investigate the impact of a highly ordered morphology on the mechanical properties. The annealed multilayer films exhibited increased toughness with decreasing layer thickness and resulted in homogeneous deformation compared to the as-extruded films. Multilayer coextrusion proved to be an advantageous method for producing continuous films with tunable mechanical response.
The phase-segregated nature of polyurethanes allows meaningful connections to be made between morphological and physical properties. We have taken advantage of this behavior by synthesizing a series ...of polyurethanes with varying extents of crystallinity and studying their morphologies in both the unstrained and deformed states, going from a completely amorphous soft segment to one with similar chemistry that displays a high extent of soft domain crystallization, thus enhancing phase segregation. The presence of dispersed semicrystalline regions within the continuous soft domain has been shown to provide a reinforcing effect when compared to that of a non-crystalline soft segment polyurethane. Incorporating a semicrystalline soft segment (PEO, 1000 g/mol) has been shown to improve overall sample toughness; however, if higher molecular weight PEO soft segments are employed (4600 g/mol), extensibility and, consequently, toughness are adversely affected due to an increased continuous domain modulus. In-situ deformation experiments demonstrate two very different deformation responses. In the copolymer-containing polyurethane (PEO−PPO−PEO, 1900 g/mol), the hard domains retain a tilted configuration up to strains of ∼450%, with only a small fraction of the hard segments undergoing reshuffling. The PEO1000-containing polyurethane, on the other hand, begins to demonstrate meridional scattering at strains of 200%, with it being the dominant peak by a strain of 300%. These two deformation behaviors are indicative of the two primary responses to deformation, which are shear and tensile, respectively. Frequently, a tensile mechanism points to decreased polyurethane mechanical properties, though this phenomenon is not seen in the series of interest.
