We have prepared new biohybrid materials based on halloysite nanotubes and natural polymers (alginate and chitosan) for the controlled and sustained release of bioactive species.

A novel green protocol for the consolidation and protection of waterlogged archeological woods with wax microparticles has been designed. First, we focused on the development of halloysite nanotubes (HNTs) based Pickering emulsions using wax as the inner phase of the oil-in-water droplets. The optimization of the preparation strategy was supported by both optical microscopy and scanning electron microscopy, which allowed us to show the morphological features of the prepared hybrid systems and their structural properties, i.e., the distribution of the clay at the interface. Also, the dependence of the overall dimensions of the prepared systems on the halloysite content was demonstrated. Microdifferential scanning calorimetry (μ-DSC) was conducted in order to assess whether the thermal properties of the wax are affected after its interaction with HNTs. Then, the Pickering emulsions were employed for the treatment of waterlogged wooden samples. Compared to the archeological woods treated with pure wax, the addition of nanotubes induced a remarkable improvement in the mechanical performance in terms of stiffness and flexural strength. The proposed protocol is environmentally friendly since water is the only solvent used throughout the entire procedure, even if wax is vehiculated into the pores at room temperature. As a consequence, the design of wax/halloysite Pickering emulsions represents a promising strategy for the preservation of wooden artworks, and it has a great potential to be scaled up, thus becoming also exploitable for the treatments of shipwrecks of large size.

In this work, we have developed a novel strategy to prepare hybrid nanostructures with controlled release properties towards khellin by exploiting the electrostatic interactions between chitosan and halloysite nanotubes (HNT). Firstly, khellin was loaded into the HNT lumen by the vacuum-assisted procedure. The drug confinement within the halloysite cavity has been proved by water contact angle experiments on the HNT/khellin tablets. Therefore, the loaded nanotubes were coated with chitosan as a consequence of the attractions between the cationic biopolymer and the halloysite outer surface, which is negatively charged in a wide pH range. The effect of the ionic strength of the aqueous medium on the coating efficiency of the clay nanotubes was investigated. The surface charge properties of HNT/khellin and chitosan/HNT/khellin nanomaterials were determined by ζ potential experiments, while their morphology was explored through Scanning Electron Microscopy (SEM). Water contact angle experiments were conducted to explore the influence of the chitosan coating on the hydrophilic/hydrophobic character of halloysite external surface. Thermogravimetry (TG) experiments were conducted to study the thermal behavior of the composite nanomaterials. The amounts of loaded khellin and coated chitosan in the hybrid nanostructures were estimated by a quantitative analysis of the TG curves. The release kinetics of khellin were studied in aqueous solvents at different pH conditions (acidic, neutral and basic) and the obtained data were analyzed by the Korsmeyer–Peppas model. The release properties were interpreted on the basis of the TG and ζ potential results. In conclusion, this study demonstrates that halloysite nanotubes wrapped by chitosan layers can be effective as drug delivery systems.