Design and fabrication of recombinant reflectin-based multilayer reflectors: bio-design engineering and photoisomerism induced wavelength modulation.

The remarkable camouflage capabilities of cephalopods have inspired many to develop dynamic optical materials which exploit certain design principles and/or material properties from cephalopod dermal cells. Here, the angle-dependent optical properties of various single-layer reflectin thin-films on Si wafers are characterized within the UV-Vis-NIR regions. Following this, initial efforts to design, fabricate, and optically characterize a bio-inspired reflectin-based multilayer reflector is described, which was found to conserve the optical properties of single layer films but exhibit reduced angle-dependent visible reflectivity. Finally, we report the integration of phytochrome visible light-induced isomerism into reflectin-based films, which was found to subtly modulate reflectin thin-film reflectivity.

The effect of terminal globular domains on the response of recombinant mini-spidroins to fiber spinning triggers.

Spider silk spidroins consist of long repetitive protein strands, flanked by globular terminal domains. The globular domains are often omitted in recombinant spidroins, but are thought to be essential for the spiders' natural spinning process. Mimicking this spinning process could be an essential step towards producing strong synthetic spider silk. Here we describe the production of a range of mini-spidroins with both terminal domains, and characterize their response to a number of biomimetic spinning triggers. Our results suggest that mini-spidroins which are able to form protein micelles due to the addition of both terminal domains exhibit shear-thinning, a property which native spidroins also show. Furthermore, our data also suggest that a pH drop alone is insufficient to trigger assembly in a wet-spinning process, and must be combined with salting-out for effective fiber formation. With these insights, we applied these assembly triggers for relatively biomimetic wet spinning. This work adds to the foundation of literature for developing improved biomimetic spinning techniques, which ought to result in synthetic silk that more closely approximates the unique properties of native spider silk.

Hierarchically Porous Silk/Activated-Carbon Composite Fibres for Adsorption and Repellence of Volatile Organic Compounds.

Fabrics comprised of porous fibres could provide effective passive protection against chemical and biological (CB) threats whilst maintaining high air permeability (breathability). Here, we fabricate hierarchically porous fibres consisting of regenerated silk fibroin (RSF) and activated-carbon (AC) prepared through two fibre spinning techniques in combination with ice-templating-namely cryogenic solution blow spinning (Cryo-SBS) and cryogenic wet-spinning (Cryo-WS). The Cryo-WS RSF fibres had exceptionally small macropores (as low as 0.1 µm) and high specific surface areas (SSAs) of up to 79 m2·g-1. The incorporation of AC could further increase the SSA to 210 m2·g-1 (25 wt.% loading) whilst also increasing adsorption capacity for volatile organic compounds (VOCs).

Graphene-aramid nanocomposite fibres via superacid co-processing.

The development of graphene-polymer nanocomposite materials has been hindered by issues such as poor colloidal stability of graphene in liquid media, weak interactions between graphene and the host polymers as well as the lack of scalable and economical graphene synthesis routes. Chlorosulfonic acid (CSA) can spontaneously disperse graphene without the need for mechanical agitation, chemical functionalisation or surfactant stabilisation,1 however is incompatible with most polymers and organic materials. Here, we demonstrate how poly(p-phenylene terephthalamide) (PPTA) - the polymer which constitutes Kevlar - can be co-processed with graphene in CSA and wet-spun into nanocomposite fibres with minimal aggregation of graphene.

Synthetic biology for fibres, adhesives and active camouflage materials in protection and aerospace.

Synthetic biology has huge potential to produce the next generation of advanced materials by accessing previously unreachable (bio)chemical space. In this prospective review, we take a snapshot of current activity in this rapidly developing area, focussing on prominent examples for high-performance applications such as those required for protective materials and the aerospace sector. The continued growth of this emerging field will be facilitated by the convergence of expertise from a range of diverse disciplines, including molecular biology, polymer chemistry, materials science and process engineering. This review highlights the most significant recent advances and address the cross-disciplinary challenges currently being faced.

Porous, Aligned, and Biomimetic Fibers of Regenerated Silk Fibroin Produced by Solution Blow Spinning.

Solution blow spinning (SBS) has emerged as a rapid and scalable technique for the production of polymeric and ceramic materials into micro-/nanofibers. Here, SBS was employed to produce submicrometer fibers of regenerated silk fibroin (RSF) from Bombyx mori (silkworm) cocoons based on formic acid or aqueous systems. Spinning in the presence of vapor permitted the production of fibers from aqueous solutions, and high alignment could be obtained by modifying the SBS setup to give a concentrated channeled airflow. The combination of SBS and a thermally induced phase separation technique (TIPS) resulted in the production of macro-/microporous fibers with 3D interconnected pores. Furthermore, a coaxial SBS system enabled a pH gradient and kosmotropic salts to be applied at the point of fiber formation, mimicking some of the aspects of the natural spinning process, fostering fiber formation by self-assembly of the spinning dope. This scalable and fast production of various types of silk-based fibrous scaffolds could be suitable for a myriad of biomedical applications.

High-Surface-Area, Emulsion-Templated Carbon Foams by Activation of polyHIPEs Derived from Pickering Emulsions.

Carbon foams displaying hierarchical porosity and excellent surface areas of >1400 m²/g can be produced by the activation of macroporous poly(divinylbenzene). Poly(divinylbenzene) was synthesized from the polymerization of the continuous, but minority, phase of a simple high internal phase Pickering emulsion. By the addition of KOH, chemical activation of the materials is induced during carbonization, producing Pickering-emulsion-templated carbon foams, or carboHIPEs, with tailorable macropore diameters and surface areas almost triple that of those previously reported. The retention of the customizable, macroporous open-cell structure of the poly(divinylbenzene) precursor and the production of a large degree of microporosity during activation leads to tailorable carboHIPEs with excellent surface areas.

Porous carbon spheres and monoliths: morphology control, pore size tuning and their applications as Li-ion battery anode materials.

The development of the next generation of advanced lithium-ion batteries (LIBs) requires new & advanced materials and novel fabrication techniques in order to push the boundaries of performance and open up new and exciting markets. Structured carbon materials, with controlled pore features on the micron and nanometer scales, are explored as advanced alternatives to conventional graphite as the active material of the LIB anode. Mesoporous carbon materials, carbon nanotube-based materials, and graphene-based materials have been extensively investigated and reviewed. Morphology control (e.g., colloids, thin films, nanofibrous mats, monoliths) and hierarchical pores (particularly the presence of large pores) exhibit an increasing influence on LIB performance. This tutorial review focuses on the synthetic techniques for preparation of porous carbon spheres and carbon monoliths, including hydrothermal carbonization, emulsion templating, ice templating and new developments in making porous carbons from sustainable biomass and metal-organic framework templating. We begin with a brief introduction to LIBs, defining key parameters and terminology used to assess the performance of anode materials, and then address synthetic techniques for the fabrication of carbon spheres & monoliths and the relevant composites, followed, respectively, by a review of their performance as LIB anode materials. The review is completed with a prospective view on the possible direction of future research in this field.

Poorly water-soluble drug nanoparticles via solvent evaporation in water-soluble porous polymers.

A generic method is described to form poorly water-soluble drug nanoparticles within water-soluble porous polymer by solvent evaporation. The simple dissolution of porous polymer with drug nanoparticles results in stable aqueous drug nanoparticle suspension under the optimized conditions. The porous polymers were prepared by freeze-drying aqueous solutions of polyvinyl alcohol, polyethylene glycol, and a surfactant. They were then used as scaffolds for the formation of nanoparticles by initially soaking them in an organic drug solution, followed with removing the solvent via evaporation under ambient conditions. This process was optimized for an antifungal drug griseofulvin, before being translated to anticonvulsant carbamazepine and antineoplastic paclitaxel via a similar procedure, with an aim to improve the loading of drug nanoparticles. By varying certain process parameters a degree of control over the particle size and surface charge could be attained, as well as the drug to stabilizer ratio (drug payload). Noticeably, aqueous paclitaxel nanoparticles (500 nm) were prepared which used the equivalent of 46% less stabilizer than the formulation Taxol.