Silvia Bittolo Bon

This article describes sensors and radio frequency (RF) components manufactured by applying selective-metallization processes (metal foil tape, liquid metal filling, electro and electroless plating, and surface embossing) to 3-D-printed and flexible dielectric substrates. All these technologies can be implemented at room temperature, thus enabling the adoption of unconventional materials and biopolymers with low glass transition temperatures. In this article, we also describe how the above technologies are used to manufacture wireless transponders for tracking and sensing applications. Several examples of RF components are reported, including antennas, beamforming networks, Doppler radars, and wireless passive transponders based on backscatter radio. Innovative circuit design approaches (such as the via-less approach) are presented and their impact on circuit manufacturing and recyclability is discussed.

Water stable proteins may offer a new field of applications in smart materials for buildings and infrastructures where hydraulic reactions are involved. In this study, cement mortars modified through water-soluble silk fibroin (SF) are proposed. Water-soluble SF obtained by redissolving SF films in phosphate buffer solution (PBS) showed the formation of a gel with β-sheet features of silk II. Electrical measurements on SF indicate that calcium ions are primarily involved in the conductivity mechanism. By exploiting the water solubility properties of silk II and Ca2+ ion transport phenomena and its trapping effect over water molecules, SF provides piezoresistive and piezocapacitive properties to cement mortars, thus enabling self-sensing of mechanical strain which is quite attractive in structural health monitoring applications. SF/cement-based composite introduces the capacitive gauge factor that surpasses the traditional resistive gauge factor reported in the literature by threefold. Cyclic voltammetry measurements demonstrated SF cement mortars possess memcapacitive behavior for positive potentials around +5 V, attributed to an interfacial charge build-up modulated by the SF concentration and the working electrode. Electrical square-biphasic excitation combined with cyclic compressive loads revealed memristive behavior during the unloading stages. These findings along with the availability and the sustainability of SF pave the way for the design of novel multifunctional materials, particularly for applications in masonry and concrete structures.

In this study, we report the preparation and characterization of water-stable films with UV-shielding and good mechanical properties, exploiting the synergistic effect of regenerated silk fibroin and bamboo-derived cellulose. Silk fibroin (SF)/bamboo (B) hybrid films are achieved by solubilizing both silk and bamboo fibers in formic acid with added CaCl₂. Infrared spectroscopy indicates that SF, when combined with bamboo, undergoes a conformational transition, providing evidence of an increase in SF crystallinity. Exploiting the intrinsic absorption of SF in the ultraviolet region, UV–Vis spectroscopy was used to assess the glass transition temperature (T_g) of SF/B films, showing a decrease in T_g by increasing the SF content. The addition of 10 wt% SF to the B matrix improved the elastic modulus by about 10% while conserving the strain at break with respect to the neat B films, increasing the UV shielding properties, while water absorption suggested the material’s hydrophilic and swelling capacity even after one month. The hybrid films showed, under solar irradiation, a photoprotective behavior on keratinocyte human cells by increasing cellular viability. These findings may find potential applications in functional fabrics.

3D printing of water stable proteins with elastic properties offers a broad range of applications including self-powered biomedical devices driven by piezoelectric biomaterials. Here, we present a study on water-soluble silk fibroin (SF) films. These films were prepared by mixing degummed silk fibers and calcium chloride (CaCl₂) in formic acid, resulting in a silk I-like conformation, which was then converted into silk II by redissolving in phosphate buffer (PBS). Circular dichroism, Raman and infrared (IR) spectroscopies were used to investigate the transitions of secondary structure in silk I and silk II as the pH of the solvent and the sonication time were changed. We showed that a solvent with low pH (e.g. 4) maintains the silk I β-turn structure; in contrast solvent with higher pH (e.g. 7.4) promotes β-sheet features of silk II. Ultrasonic treatment facilitates the transition to water stable silk II only for the SF redissolved in PBS. SF from pH 7.4 solution has been printed using extrusion-based 3D printing. A self-powered memristor was realized, comprising an SF-based electric generator and an SF 3D-printed memristive unit connected in series. By exploiting the piezoelectric properties of silk II with higher β-sheet content and Ca²⁺ ion transport phenomena, the application of an input voltage driven by a SF generator to SF 3D printed holey structures induces a variation from an initial low resistance state (LRS) to a high resistance state (HRS) that recovers in a few minutes, mimicking the transient memory, also known as short-term memory. Thanks to this holistic approach, these findings can contribute to the development of self-powered neuromorphic networks based on biomaterials with memory capabilities.

Despite the technological importance of semiconductor black phosphorus (BP) in materials science, maintaining the stability of BP crystals in organic media and protecting them from environmental oxidation remains challenging. In this study, we present the synthesis of bulk BP and the exploitation of the viscoelastic properties of a regenerated silk fibroin (SF) film as a biocompatible substrate to transfer BP flakes, thereby preventing oxidation. A model based on the flow of polymers revealed that the applied flow-induced stresses exceed the yield stress of the BP aggregate. Raman spectroscopy was used to investigate the exfoliation efficiency as well as the environmental stability of BP transferred on the SF substrate. Notably, BP flakes transferred to the SF substrate demonstrated improved stability when SF was dissolved in a phosphate-buffered saline medium, and in vitro cancer cell viability experiments demonstrate the tumor ablation efficiency under visible to near-infrared (Vis-nIR) radiation. Moreover, the SF and BP-enriched SF (SF/BP) solution was shown to be processable via extrusion-based three-dimensional (3D) printing. Therefore, this work paves the way for a general method for the transferring of BP on natural biodegradable polymers and processing them via 3D printing toward novel functionalities and complex shapes for biomedical purposes.

Four-dimensional (4D) printing is an innovative additive manufacturing technology used to fabricate structures that can evolve over time when exposed to a predefined environmental stimulus. 4D printed objects are no longer static objects but programmable active structures that accomplish their functions thanks to a change over time in their physical/chemical properties that usually displays macroscopically as a shapeshifting in response to an external stimulus. 4D printing is characterized by several entangled features (e.g., involved material(s), structure geometry, and applied stimulus entities) that need to be carefully coupled to obtain a favorable fabrication and a functioning structure. Overall, the integration of micro-/nanofabrication methods of biomaterials with nanomaterials represents a promising approach for the development of advanced materials. The ability to construct complex and multifunctional triggerable structures capable of being activated allows for the control of biomedical device activity, reducing the need for invasive interventions. Such advancements provide new tools to biomedical engineers and clinicians to design dynamically actuated implantable devices. In this context, the aim of this review is to demonstrate the potential of 4D printing as an enabling manufacturing technology to code the environmentally triggered physical evolution of structures and devices of biomedical interest.

In this study, regenerated silk (RS) obtained from Bombyx Mori cocoons is compounded with carboxyl-functionalized carbon nanotubes (f-CNTs) in an aqueous environment for the fabrication of functional bio-adhesives. Molecular interactions between RS and carboxyl groups of CNTs result in structural increase of the β-sheet formation, obtaining a resistant adhesive suitable for a wet biological substrate. Moreover, the functionalization of CNTs promotes their dispersion in RS, thus enabling the production of films with controlled electrical conductivity. The practical utility of such a property is demonstrated through the fabrication of a piezoelectric device implanted in a rat to monitor the breathing in vivo and to be used as a self-powered system. Finally, RS/f-CNTs were used as a printable biomaterial ink to three dimensionally print bilayer hollow tubular structures composed of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and RS. Initial tests carried out by seeding and growing human skin fibroblasts demonstrated that the 3D printed bilayer hollow cylindrical structures offer a suitable surface for the seeded cells to attach and proliferate. In general, the herein proposed RS/f-CNT composite serves as a versatile material for solvent-free dispersion processing and 3D printing, thus paving a new approach to prepare multifunctional materials with potential applications of great interest in sealing biological substrates and implantable devices for regenerative medicine.

From the global spread of COVID-19 we learned that SARS-CoV-2 virus can be transmitted via respiratory liquid droplets. In this study, we performed first-principles calculations suggesting that water molecules once in contact with the graphene oxide (GO) layer interact with its functional groups, therefore, developing an electric field induced by the heterostructure formation. Experiments on GO polymer composite film supports the theoretical findings, showing that the interaction with water aerosol generates a voltage output signal of up to −2 V. We then developed an electrostatic composite fiber by the coagulation method mixing GO with poly(methyl methacrylate) (PMMA). These findings could be used to design protective fabrics with antiviral activity against negatively charged spike proteins of airborne viruses.

Manual and mechanical suturing are currently the gold standard for bowel anastomosis. If tissue approximation fails, anastomotic leaks occur. Anastomotic leaks may have catastrophic consequences. The development of a fully absorbable, biocompatible sealant material based on a bio-ink silk fibroin can reduce the chance of anastomotic leaks. We have produced a Ca-modified plasticised regenerated silk (RS) with gold nanorods sealant. This sealant was applied to anastomosed porcine intestine. Water absorption from wet tissue substrate applied compressive strains on hybrid RS films. This compression results in a sealant effect on anastomosis. The increased toughness of the hybrid plasticised RS resulted in the designing of a bio-film with superior elongation at break (i.e., ≈200%) and bursting pressure. We have also reported structure-dependent piezoelectricity of the RS film that shows a piezoelectric effect out of the plane. We hope that in the future, bowel anastomosis can be simplified by providing a multifunctional bio-film that makes feasible the mechanical tissue joint without the need for specific tools and could be used in piezoelectric sealant heads.