Self-assembly of molecular units into complex and functional superstructures is ubiquitous in biology. The number of superstructures realized by self-assembly of man-made nanoscale units is also growing. However, assemblies of colloidal inorganic nanocrystals [1][2][3] are still at an elementary level, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we show how monodisperse colloidal octapod-shaped nanocrystals self-assemble, in a suitable solution environment, on two sequential levels. First, linear chains of interlocked octapods are formed, and subsequently the chains spontaneously self-assemble into threedimensional superstructures. Remarkably, all the instructions for the hierarchical self-assembly are encoded in the octapod shape. The mechanical strength of these superstructures is improved by welding the constituent nanocrystals together.The organization of colloidal nanocrystals into ordered structures is a necessary step towards the fabrication of artificial solids and new devices. Superstructures can be built either by self-assembly directly in solution, or on a substrate following solvent evaporation or de-wetting [4][5][6] . A variety of forces can be involved in their formation: van der Waals (vdW) attractions between the particles, steric repulsions between the hydrophobic tails of the surfactants (often coating the nanocrystal surface), capillary forces during solvent evaporation, attractive depletion forces, Coulomb forces between surface charges or electric dipoles, and magnetic forces 1,3,5,[7][8][9][10][11][12] . The assembly of many ordered threedimensional (3D) superstructures, for example, simple, binary, or ternary assemblies of spherical nanoparticles [13][14][15][16][17] , and smectic-like multilayers of hexagonally packed nanorods 18 , as well as liquid crystalline phases, is found to be solely driven by entropy [19][20][21] . More elaborate assemblies could be achieved from such simple building blocks by encoding information for the self-assembly in the surface pattern of the nanoparticles, for instance by DNA functionalization to modify the strength and directionality of particle-particle interactions [22][23][24] . Furthermore, bifunctional linkers and key-lock molecular pairs have been employed to align nanorods in chain-like structures 25 . Directional electric and/or solvophobic interactions were further employed to drive the organization of spherical nanoparticles into lattices 26 . Finally, templating has been successfully applied to create hierarchical superstructures using principally spherical particles 27,28 limits to the quality and reproducibility of such assemblies and to their maximum attainable size.Branched nanocrystals such as tetrapod or octapod-shaped colloidal nanoparticles have recently emerged as promising materials for photovoltaics and electronics 27,28,30,31 , and questions have been rai...

In this work is presented a new category of self-growing, fibrous, natural composite materials with controlled physical properties that can be produced in large quantities and over wide areas, based on mycelium, the main body of fungi. Mycelia from two types of edible, medicinal fungi, Ganoderma lucidum and Pleurotus ostreatus, have been carefully cultivated, being fed by two bio-substrates: cellulose and cellulose/potato-dextrose, the second being easier to digest by mycelium due to presence of simple sugars in its composition. After specific growing times the mycelia have been processed in order to cease their growth. Depending on their feeding substrate, the final fibrous structures showed different relative concentrations in polysaccharides, lipids, proteins and chitin. Such differences are reflected as alterations in morphology and mechanical properties. The materials grown on cellulose contained more chitin and showed higher Young’s modulus and lower elongation than those grown on dextrose-containing substrates, indicating that the mycelium materials get stiffer when their feeding substrate is harder to digest. All the developed fibrous materials were hydrophobic with water contact angles higher than 120°. The possibility of tailoring mycelium materials’ properties by properly choosing their nutrient substrates paves the way for their use in various scale applications.

Poly(vinylidene fluoride-trifluoroethylene, P(VDF-TrFE)) and P(VDF-TrFE)/barium titanate nanoparticle (BTNP) films are prepared and tested as substrates for neuronal stimulation through direct piezoelectric effect. Films are characterized in terms of surface, mechanical, and piezoelectric features before in vitro testing on SH-SY5Y cells. In particular, BTNPs significantly improve piezoelectric properties of the films (4.5-fold increased d31 ). Both kinds of films support good SH-SY5Y viability and differentiation. Ultrasound (US) stimulation is proven to elicit Ca(2+) transients and to enhance differentiation in cells grown on the piezoelectric substrates. For the first time in the literature, this study demonstrates the suitability of polymer/ceramic composite films and US for neuronal stimulation through direct piezoelectric effect.

Bioplastics with a wide range of mechanical properties were directly obtained from industrially processed edible vegetable and cereal wastes. As model systems, we present bioplastics synthesized from wastes of parsley and spinach stems, rice hulls, and cocoa pod husks by digesting in trifluoroacetic acid (TFA), casting, and evaporation. In this way, amorphous cellulose-based plastics are formed. Moreover, many other natural elements present in these plants are carried over into the bioplastics rendering them with many exceptional thermo-physical properties. Here, we show that, due to their broad compatibility with cellulose, amorphous cellulose can be naturally plasticized with these bioplastics by simply mixing during processing. Comparison of their mechanical properties with that of various petroleum based synthetic polymers indicates that these bioplastics have equivalent mechanical properties to the nondegrading ones. This opens up possibilities for replacing some of the nondegrading polymers with the present bioplastics obtained from agro-waste.

Stretchable capacitive devices are instrumental for new‐generation multifunctional haptic technologies particularly suited for soft robotics and electronic skin applications. A majority of elongating soft electronics still rely on silicone for building devices or sensors by multiple‐step replication. In this study, fabrication of a reliable elongating parallel‐plate capacitive touch sensor, using nitrile rubber gloves as templates, is demonstrated. Spray coating both sides of a rubber piece cut out of a glove with a conductive polymer suspension carrying dispersed carbon nanofibers (CnFs) or graphene nanoplatelets (GnPs) is sufficient for making electrodes with low sheet resistance values (≈10 Ω sq−1). The electrodes based on CnFs maintain their conductivity up to 100% elongation whereas the GnPs‐based ones form cracks before 60% elongation. However, both electrodes are reliable under elongation levels associated with human joints motility (≈20%). Strikingly, structural damages due to repeated elongation/recovery cycles could be healed through annealing. Haptic sensing characteristics of a stretchable capacitive device by wrapping it around the fingertip of a robotic hand (ICub) are demonstrated. Tactile forces as low as 0.03 N and as high as 5 N can be easily sensed by the device under elongation or over curvilinear surfaces.

Designing starch-based biopolymers and biodegradable composites with durable mechanical properties and good resistance to water is still a challenging task. Although thermoplastic (destructured) starch has emerged as an alternative to petroleum-based polymers, its poor dimensional stability under humid and dry conditions extensively hinders its use as the biopolymer of choice in many applications. Unmodified starch granules, on the other hand, suffer from incompatibility, poor dispersion, and phase separation issues when compounded into other thermoplastics above a concentration level of 5%. Herein, we present a facile biodegradable elastomer preparation method by incorporating large amounts of unmodified corn starch, exceeding 80% by volume, in acetoxy-polyorganosiloxane thermosets to produce mechanically robust, hydrophobic bioelastomers. The naturally adsorbed moisture on the surface of starch enables autocatalytic rapid hydrolysis of polyorganosiloxane to form Si-O-Si networks. Depending on the amount of starch granules, the mechanical properties of the bioelastomers can be easily tuned with high elastic recovery rates. Moreover, starch granules considerably lowered the surface friction coefficient of the polyorganosiloxane network. Stress relaxation measurements indicated that the bioelastomers have strain energy dissipation factors that are lower than those of conventional rubbers, rendering them as promising green substitutes for plastic mechanical energy dampeners. Corn starch granules also have excellent compatibility with addition-cured polysiloxane chemistry that is used extensively in microfabrication. Regardless of the starch concentration, all of the developed bioelastomers have hydrophobic surfaces with lower friction coefficients and much less water uptake capacity than those of thermoplastic starch. The bioelastomers are biocompatible and are estimated to biodegrade in Mediterranean seawater within three to six years.

Electrically conductive materials based on cotton have important implications for wearable electronics. We have developed flexible and conductive cotton fabrics (∼10 Ω/sq) by impregnation with graphene and thermoplastic polyurethane-based dispersions. Nanocomposite fabrics display remarkable resilience against weight-pressed severe folding as well as laundry cycles. Folding induced microcracks can be healed easily by hot-pressing, restoring initial electrical conductivity. Impregnated cotton fabric conductors demonstrate better mechanical properties compared to pure cotton and thermoplastic polyurethane maintaining breathability. They also resist environmental aging such as solar irradiation and high humidity.

The global production of thermosets has been increasing in recent years causing rapid consumption of fossil-based feedstocks and contributing to the plastic waste accumulation in the environment, especially because they cannot be easily reprocessed or recycled at the end of their lifetime. These drawbacks can only be overcome with the development of environmentally friendly, recyclable thermosets from renewable resources. For this reason, we present a facile way to produce a biobased reprocessable thermoset, a vitrimer, by thiol-acrylate coupling between epoxidized soybean oil acrylate and a diboronic ester dithiol dynamic cross-linker. The synthesis of the cross-linker and all the processes for the production of the vitrimer has been done following green chemistry principles. The developed vitrimer material can be reprocessed multiple times like a thermoplastic, without compromising its mechanical properties. Moreover, it can be conveniently recycled by reversible hydrolysis in 90% ethanol and subsequent solvent evaporation, regenerating the original vitrimer. An important advantage of the developed material, especially regarding its applications, is that it is able to self-repair mechanical abrasion-related defects, like scratches and cuts, at room temperature, thanks to the low glass transition temperature and rapid boronic ester exchange, which enables it to demonstrate great potential as a self-healing coating. In case of an accidental release into the environment, it is able to biodegrade, solving the problem of waste accumulation.