Silk fibroin molecularly imprinted nanoparticles as biocompatible molecular nanotraps: Molecular recognition ties the knot with biomaterials. The bioMIP’s labeling and degradation

Molecularly imprinted nanoparticles (nanoMIPs) are biomimetic polymeric nanomaterials, typically prepared from acrylamide and derivatives, that are formed by a template-assisted synthesis. NanoMIPs display high afnity, selectivity, and specifcity for the targeted molecule, on the par of natural receptors and antibodies. Recently, we introduced a paradigmatic change by forming nanoMIPs starting from biomaterials, under the name of bioMIPs, as a strategy to promptly translate them into the clinical settings. Silk fbroin, that is a biocompatible and non-immunogenic natural material, was used as a building block for the synthesis of bioMIPs tailored to recognize the protein human serum albumin. BioMIPs confrmed high selectivity and specifcity for the targeted protein, together with cytocompatibility. The present work expands the actual knowledge on bioMIPs, studying a route to post-synthetically entail fuorescent tags, with the aim to localize these molecular nanotraps in cells and tissues. Moreover, the enzymatic degradation of bioMIPs was investigated, to support the role of bioMIPs as greener and biocompatible alternatives to non-natural biomimetics

Biofunctional Silk Kirigami With Engineered Properties.

The fabrication of multifunctional materials that interface with living environments is a problem of great interest. A variety of structural design concepts have been integrated with functional materials to form biodevices and surfaces for health monitoring. In particular, approaches based on kirigami-inspired cuts can engineer flexibility in materials through the creation of patterned defects. Here, the fabrication of a biodegradable and biofunctional "silk kirigami" material is demonstrated. Mechanically flexible, free-standing, optically transparent, large-area biomaterial sheets with precisely defined and computationally designed microscale cuts can be formed using a single-step photolithographic process. Using modeling techniques, it is shown how cuts can generate remarkable "self-shielding" leading to engineered elastic behavior and deformation. As composites with conducting polymers, flexible, intrinsically electroactive sheets can be formed. Importantly, the silk kirigami sheets are biocompatible, can serve as substrates for cell culture, and be proteolytically resorbed. The unique properties of silk kirigami suggest a host of applications as transient, "green", functional biointerfaces, and flexible bioelectronics

Nano-Hydroxyapatite Derived from Biogenic and Bioinspired Calcium Carbonates: Synthesis and In Vitro Bioactivity

Biogenic calcium carbonates naturally contain ions that can be beneficial for bone regeneration and therefore are attractive resources for the production of bioactive calcium phosphates. In the present work, cuttlefish bones, mussel shells, chicken eggshells and bioinspired amorphous calcium carbonate were used to synthesize hydroxyapatite nano-powders which were consolidated into cylindrical pellets by uniaxial pressing and sintering 800–1100 °C. Mineralogical, structural and chemical composition were studied by SEM, XRD, inductively coupled plasma/optical emission spectroscopy (ICP/OES). The results show that the phase composition of the sintered materials depends on the Ca/P molar ratio and on the specific CaCO3 source, very likely associated with the presence of some doping elements like Mg2+ in eggshell and Sr2+ in cuttlebone. Different CaCO3 sources also resulted in variable densification and sintering temperature. Preliminary in vitro tests were carried out (by the LDH assay) and they did not reveal any cytotoxic effects, while good cell adhesion and proliferation was observed at day 1, 3 and 5 after seeding through confocal microscopy. Among the different tested materials, those derived from eggshells and sintered at 900 °C promoted the best cell adhesion pattern, while those from cuttlebone and amorphous calcium carbonate showed round-shaped cells and poorer cell-to-cell interconnection

Nano-Hydroxyapatite Derived from Biogenic and Bioinspired Calcium Carbonates: Synthesis and In Vitro Bioactivity

Biogenic calcium carbonates naturally contain ions that can be beneficial for bone regeneration and therefore are attractive resources for the production of bioactive calcium phosphates. In the present work, cuttlefish bones, mussel shells, chicken eggshells and bioinspired amorphous calcium carbonate were used to synthesize hydroxyapatite nano-powders which were consolidated into cylindrical pellets by uniaxial pressing and sintering 800–1100 °C. Mineralogical, structural and chemical composition were studied by SEM, XRD, inductively coupled plasma/optical emission spectroscopy (ICP/OES). The results show that the phase composition of the sintered materials depends on the Ca/P molar ratio and on the specific CaCO3 source, very likely associated with the presence of some doping elements like Mg2+ in eggshell and Sr2+ in cuttlebone. Different CaCO3 sources also resulted in variable densification and sintering temperature. Preliminary in vitro tests were carried out (by the LDH assay) and they did not reveal any cytotoxic effects, while good cell adhesion and proliferation was observed at day 1, 3 and 5 after seeding through confocal microscopy. Among the different tested materials, those derived from eggshells and sintered at 900 °C promoted the best cell adhesion pattern, while those from cuttlebone and amorphous calcium carbonate showed round-shaped cells and poorer cell-to-cell interconnection

Silk fibroin-based inks for in situ 3D printing using a double crosslinking process

The shortage of tissues and organs for transplantation is an urgent clinical concern. In situ 3D printing is an advanced 3D printing technique aimed at printing the new tissue or organ directly in the patient. The ink for this process is central to the outcomes, and must meet specific requirements such as rapid gelation, shape integrity, stability over time, and adhesion to surrounding healthy tissues. Among natural materials, silk fibroin exhibits fascinating properties that have made it widely studied in tissue engineering and regenerative medicine. However, further improvements in silk fibroin inks are needed to match the requirements for in situ 3D printing. In the present study, silk fibroin-based inks were developed for in situ applications by exploiting covalent crosslinking process consisting of a pre-photo-crosslinking prior to printing and in situ enzymatic crosslinking. Two different silk fibroin molecular weights were characterized and the synergistic effect of the covalent bonds with shear forces enhanced the shift in silk secondary structure toward β-sheets, thus, rapid stabilization. These hydrogels exhibited good mechanical properties, stability over time, and resistance to enzymatic degradation over 14 days, with no significant changes over time in their secondary structure and swelling behavior. Additionally, adhesion to tissues in vitro was demonstrated

Silk Fibroin Film Decorated with Ultralow FeCo Content by Sputtering Deposition Results in a Flexible and Robust Biomaterial for Magnetic Actuation

Magnetically responsive soft biomaterials are at the forefront of bioengineering and biorobotics. We have created a magnetic hybrid material by coupling silk fibroin-i.e., a natural biopolymer with an optimal combination of biocompatibility and mechanical robustness-with the FeCo alloy, the ferromagnetic material with the highest saturation magnetization. The material is in the form of a 6 micron-thick silk fibroin film, coated with a FeCo layer (nominal thickness: 10 nm) grown by magnetron sputtering deposition. The sputtering deposition technique is versatile and eco-friendly and proves effective for growing the magnetic layer on the biopolymer substrate, also allowing one to select the area to be decorated. The hybrid material is biocompatible, lightweight, flexible, robust, and water-resistant. Electrical, structural, mechanical, and magnetic characterization of the material, both as-prepared and after being soaked in water, have provided information on the adhesion between the silk fibroin substrate and the FeCo layer and on the state of internal mechanical stresses. The hybrid film exhibits a high magnetic bending response under a magnetic field gradient, thanks to an ultralow fraction of the FeCo component (less than 0.1 vol %, i.e., well below 1 wt %). This reduces the risk of adverse health effects and makes the material suitable for bioactuation applications