The high versatility of poly(vinylpyrrolidone) (PVP) can be explained by its diverse properties including its solubility in water and in a broad range of liquid media, high chemical and thermal resistance, and unique wetting, binding, and film-forming properties. Thanks to biocompatibility, absence of toxicity and high capacity to form interpolymer complexes, PVP is widely used for designing materials for different applications, such as biomaterials for medical and nonmedical uses. This review summarizes a vast diversity of applicative examples showing the tremendous opportunities for future research and developments of PVP based biomaterials. GRAPHICAL ABSTRACT

Polysaccharides and proteins are abundantly found in nature and are highly recommended for developing eco-friendly materials due to their special properties (biodegradability, biocompatibility, non-toxicity, low cost, etc.). However, they sometimes fail to meet specific requirements due to poor mechanical and physical properties. Poly(vinyl alcohol) (PVA) is one of the promising synthetic polymers with superior properties that can be blended with natural polymers for obtaining novel biomaterials with improved performances. This review addresses recent advance in PVA/polysaccharides and PVA/proteins biocomposites design and fabrication, mainly for the past two decades.

Poly(vinyl alcohol) (PVA) is a versatile synthetic polymer, used for the design of hydrogels, porous membranes and films. Its solubility in water, film- and hydrogel-forming capabilities, non-toxicity, crystallinity and excellent mechanical properties, chemical inertness and stability towards biological fluids, superior oxygen and gas barrier properties, good printability and availability (relatively low production cost) are the main aspects that make PVA suitable for a variety of applications, from biomedical and pharmaceutical uses to sensing devices, packaging materials or wastewater treatment. However, pure PVA materials present low stability in water, limited flexibility and poor biocompatibility and biodegradability, which restrict its use alone in various applications. PVA mixed with other synthetic polymers or biomolecules (polysaccharides, proteins, peptides, amino acids etc.), as well as with inorganic/organic compounds, generates a wide variety of materials in which PVA’s shortcomings are considerably improved, and new functionalities are obtained. Also, PVA’s chemical transformation brings new features and opens the door for new and unexpected uses. The present review is focused on recent advances in PVA-based hydrogels.

Over the last decade, efforts have been oriented toward the development of suitable gels for 3D printing, with controlled morphology and shear-thinning behavior in well-defined conditions. As a multidisciplinary approach to the fabrication of complex biomaterials, 3D bioprinting combines cells and biocompatible materials, which are subsequently printed in specific shapes to generate 3D structures for regenerative medicine or tissue engineering. A major interest is devoted to the printing of biomimetic materials with structural fidelity after their fabrication. Among some requirements imposed for bioinks, such as biocompatibility, nontoxicity, and the possibility to be sterilized, the nondamaging processability represents a critical issue for the stability and functioning of the 3D constructs. The major challenges in the field of printable gels are to mimic at different length scales the structures existing in nature and to reproduce the functions of the biological systems. Thus, a careful investigation of the rheological characteristics allows a fine-tuning of the material properties that are manufactured for targeted applications. The fluid-like or solid-like behavior of materials in conditions similar to those encountered in additive manufacturing can be monitored through the viscoelastic parameters determined in different shear conditions. The network strength, shear-thinning, yield point, and thixotropy govern bioprintability. An assessment of these rheological features provides significant insights for the design and characterization of printable gels. This review focuses on the rheological properties of printable bioinspired gels as a survey of cutting-edge research toward developing printed materials for additive manufacturing.