Bioinspired strategy to reinforce PVA with improved toughness and thermal properties via hydrogen-bond self-assembly

Despite the high strength and stiffness of polymer nanocomposites, they usually display lower deformability and toughness relative to their matrices. Spider silk features exceptionally high stiffness and toughness via the hierarchical architecture based on hydrogen-bond (H-bond) assembly. Inspired by this intriguing phenomenon, we here exploit melamine (MA) to reinforce poly(vinyl alcohol) (PVA) via H-bond self-assembly at a molecular level. Our results have shown that due to the formation of physical cross-link network based on H-bond assembly between MA and PVA, yield strength, Young’s modulus, extensibility, and toughness of PVA are improved by 22, 25, 144, and 200% with 1.0 wt % MA, respectively. Moreover, presence of MA can enhance the thermal stability of PVA to a great extent, even exceeding some nanofillers (e.g., graphene). This work provides a facile method to improve the mechanical properties of polymers via H-bond self-assembly.

Bioinspired strategy for tuning thermal stability of PVA via hydrogen-bond crosslink

Although many approaches have been employed to enhance thermal stability of PVA, developing a facile and effective strategy remains highly attractive. Herein, we demonstrate a highly effective approach to strikingly improve thermal stability of PVA by selecting the types of multiamines molecules to tune the hydrogen-bond crosslink density. Results show that only adding 0.5 wt% of 2,4,5,6-tetraaminopyrimidine can make the initial degradation temperature (Ti) and maximum degradation temperature (Tmax) of PVA increase by ~55 °C and 98 °C due to the formation of 3D physically H-bond crosslinked network, resulting in superior thermal stability property to those of PVA nanocomposites. Moreover, thermal stability strongly depends on the H-bond crosslink density, and Ti and Tmax basically obey the linear hydrogen-bond relations despite some deviations. This work opens up a novel biological methodology for creating thermally stable polymeric materials.

N7-(carboxymethyl)guanine-lithium crystalline complex: a bioinspired solid electrolyte

Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it's in-built supply of Li(+)-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10(-7) to 10(-3) Ω(-1) cm(-1)) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80-100 °C, from a dual Li(+) and H(+) (<100 °C) to a pure Li(+) conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries.

Superhydrophobic polyimide films with a hierarchical topography : combined replica molding and layer-by-layer assembly

Artificial superhydrophobic surfaces with a hierarchical topography were fabricated by using layer-by-layer assembly of polyelectrolytes and silica nanoparticles on microsphere-patterned polyimide precursor substrates followed with thermal and fluoroalkylsilane treatment. In this special hierarchical topography, micrometer-scale structures were provided by replica molding of polyamic acid using two-dimensional arrays of polystyrene latex spheres as templates, and nanosized silica particles were then assembled on these microspheres to construct finer structures at the nanoscale. Heat treatment was conducted to induce chemical cross-linking between polyelectrolytes and simultaneously convert polyamic acid to polyimide. After surface modification with fluoroalkylsilane, the as-prepared highly hydrophilic surface was endowed with superhydrophobicity due to the bioinspired combination of low surface energy materials and hierarchical surface structures. A superhydrophobic surface with a static water contact angle of 160 degrees and sliding angle of less than 10 degrees was obtained. Notably, the polyimide microspheres were integrated with the substrate and were mechanically stable. In addition, the chemical and mechanical stability of the polyelectrolyte/silica nanoparticle multilayers could be increased by heat-induced cross-linking between polyelectrolytes to form nylon-like films, as well as the formation of interfacial chemical bonds.

Bio-inspired hydrogen-bond cross-link strategy toward strong and tough polymeric materials

It remains a huge challenge to create advanced polymeric materials combining high strength, great toughness, and biodegradability so far. Despite enhanced strength and stiffness, biomimetic materials and polymer nanocomposites suffer notably reduced extensibility and toughness when compared to polymer bulk. Silk displays superior strength and toughness via hydrogen bonds (H-bonds) assembly, while cuticles of mussels gain high hardness and toughness via metal complexation cross-linking. Here, we propose a H-bonds cross-linking strategy that can simultaneously strikingly enhance strength, modulus, toughness, and hardness relative to polymer bulk. The H-bond cross-linked poly(vinyl alcohol) exhibits high yield strength (140 MPa), reduced modulus (22.5 GPa) in nanoindention tests, hardness (0.5 GPa), and great extensibility (40%). More importantly, there exist semiquantitive linear relationships between the number of effective H-bond and macroscale properties. This work suggests a promising methodology of designing advanced materials with exceptional mechanical by adding low amounts (1.0 wt %) of small molecules multiamines serving as H-bond cross-linkers.

Characterisation of minimalist co-assembled fluorenylmethyloxycarbonyl self-assembling peptide systems for presentation of multiple bioactive peptides

The nanofibrillar structures that underpin self-assembling peptide (SAP) hydrogels offer great potential for the development of finely tuned cellular microenvironments suitable for tissue engineering. However, biofunctionalisation without disruption of the assembly remains a key issue. SAPS present the peptide sequence within their structure, and studies to date have typically focused on including a single biological motif, resulting in chemically and biologically homogenous scaffolds. This limits the utility of these systems, as they cannot effectively mimic the complexity of the multicomponent extracellular matrix (ECM). In this work, we demonstrate the first successful co-assembly of two biologically active SAPs to form a coassembled scaffold of distinct two-component nanofibrils, and demonstrate that this approach is more bioactive than either of the individual systems alone. Here, we use two bioinspired SAPs from two key ECM proteins: Fmoc-FRGDF containing the RGD sequence from fibronectin and Fmoc-DIKVAV containing the IKVAV sequence from laminin. Our results demonstrate that these SAPs are able to co-assemble to form stable hybrid nanofibres containing dual epitopes. Comparison of the co-assembled SAP system to the individual SAP hydrogels and to a mixed system (composed of the two hydrogels mixed together post-assembly) demonstrates its superior stable, transparent, shear-thinning hydrogels at biological pH, ideal characteristics for tissue engineering applications. Importantly, we show that only the coassembled hydrogel is able to induce in vitro multinucleate myotube formation with C2C12 cells. This work illustrates the importance of tissue engineering scaffold functionalisation and the need to develop increasingly advanced multicomponent systems for effective ECM mimicry.

STATEMENT OF SIGNIFICANCE: Successful control of stem cell fate in tissue engineering applications requires the use of sophisticated scaffolds that deliver biological signals to guide growth and differentiation. The complexity of such processes necessitates the presentation of multiple signals in order to effectively mimic the native extracellular matrix (ECM). Here, we establish the use of two biofunctional, minimalist self-assembling peptides (SAPs) to construct the first co-assembled SAP scaffold. Our work characterises this construct, demonstrating that the physical, chemical, and biological properties of the peptides are maintained during the co-assembly process. Importantly, the coassembled system demonstrates superior biological performance relative to the individual SAPs, highlighting the importance of complex ECM mimicry. This work has important implications for future tissue engineering studies.