Theories have been put forward on the etiology of sialoliths; however, a comprehensive understanding of their growth mechanisms is lacking. In an attempt to fill this gap, the current study has evaluated the internal architecture and growth patterns of a set of 30 independent specimens of sialoliths characterized at different scales by computed microtomography and electron microscopy. Tomography reconstructions showed cores in most of the sialoliths. The cores were surrounded by concentric or irregular patterns with variable degrees of mineralization. Regardless of the patterns, at finer scales the sialoliths consisted of banded and globular structures. The distribution of precipitates in the banded structures is compatible with a Liesegang–Ostwald phenomenon. On the other hand, the globular structures appear to arise from surface tension effects and to develop self-similar features as a result of a viscous fingering process. Electron diffraction patterns demonstrated that Ca- and P-based electrolytes crystallize in a structure close to that of hydroxyapatite. The organic matter contained sulfur with apparent origin from sulfated components of secretory material. These results cast new light on the mechanisms involved in the formation of sialoliths.

The development of new materials that mimic cartilage and its function is an unmet need that will allow replacing the damaged parts of the joints, instead of the whole joint. Polyvinyl alcohol (PVA) hydrogels have raised special interest for this application due to their biocompatibility, high swelling capacity and chemical stability. In this work, the effect of post-processing treatments (annealing, high hydrostatic pressure (HHP) and gamma-radiation) on the performance of PVA gels obtained by cast-drying was investigated and, their ability to be used as delivery vehicles of the anti-inflammatories diclofenac or ketorolac was evaluated. HHP damaged the hydrogels, breaking some bonds in the polymeric matrix, and therefore led to poor mechanical and tribological properties. The remaining treatments, in general, improved the performance of the materials, increasing their crystallinity. Annealing at 150 °C generated the best mechanical and tribological results: higher resistance to compressive and tensile loads, lower friction coefficients and ability to support higher loads in sliding movement. This material was loaded with the anti-inflammatories, both without and with vitamin E (Vit.E) or Vit.E + cetalkonium chloride (CKC). Vit.E + CKC helped to control the release of the drugs which occurred in 24 h. The material did not induce irritability or cytotoxicity and, therefore, shows high potential to be used in cartilage replacement with a therapeutic effect in the immediate postoperative period.

Lithotripsy methods show relatively low efficiency in the fragmentation of sialoliths compared with the success rates achieved in the destruction of renal calculi. However, the information available on the mechanical behavior of sialoliths is limited and their apparently tougher response is not fully understood. This work evaluates the hardness and Young's modulus of sialoliths at different scales and analyzes specific damage patterns induced in these calcified structures by ultrasonic vibrations, pneumoballistic impacts, shock waves, and laser ablation. A clear correlation between local mechanical properties and ultrastructure/chemistry has been established: sialoliths are composite materials consisting of hard and soft components of mineralized and organic nature, respectively. Ultrasonic and pneumoballistic reverberations damage preferentially highly mineralized regions, leaving relatively unaffected the surrounding organic matter. In contrast, shock waves leach the organic component and lead to erosion of the overall structure. Laser ablation destroys homogeneously the irradiated zones regardless of the mineralized/organic nature of the underlying ultrastructure; however, damage is less extensive than with mechanical methods. Overall, the present results show that composition and internal structure are key features behind sialoliths' comminution behavior and that the organic matter contributes to reduce the therapeutic efficiency of lithotripsy methods.

Polyvinyl alcohol (PVA) hydrogels have been widely studied for cartilage replacement due to their biocompatibility, chemical stability, and ability to be modified such that they approximate natural tissue behavior. Additionally, they may also be used with advantages as local drug delivery systems. However, their properties are not yet the most adequate for such applications. This work aimed to develop new PVA-based hydrogels for this purpose, displaying improved tribomechanical properties with the ability to control the release of diclofenac (DFN). Four types of PVA-based hydrogels were prepared via freeze-thawing: PVA, PVA/PAA (by polyacrylic acid (PAA) addition), PVA/PAA+PEG (by polyethylene glycol (PEG) immersion), and PVA/PAA+PEG+A (by annealing). Their morphology, water uptake, mechanical and rheological properties, wettability, friction coefficient, and drug release behavior were accessed. The irritability of the best-performing material was investigated. The results showed that the PAA addition increased the swelling and drug release amount. PEG immersion led to a more compact structure and significantly improved the material’s tribomechanical performance. The annealing treatment led to the material with the most suitable properties: besides presenting a low friction coefficient, it further enhanced the mechanical properties and ensured a controlled DFN release for at least 3 days. Moreover, it did not reveal irritability potential for biological tissues.