Block Copolymers in 3D/4D Printing: Advances and Applications as Biomaterials.

3D printing is a manufacturing technique in constant evolution. Day by day, new materials and methods are discovered, making 3D printing continually develop. 3D printers are also evolving, giving us objects with better resolution, faster, and in mass production. One of the areas in 3D printing that has excellent potential is 4D printing. It is a technique involving materials that can react to an environmental stimulus (pH, heat, magnetism, humidity, electricity, and light), causing an alteration in their physical or chemical state and performing another function. Lately, 3D/4D printing has been increasingly used for fabricating materials aiming at drug delivery, scaffolds, bioinks, tissue engineering (soft and hard), synthetic organs, and even printed cells. The majority of the materials used in 3D printing are polymeric. These materials can be of natural origin or synthetic ones of different architectures and combinations. The use of block copolymers can combine the exemplary properties of both blocks to have better mechanics, processability, biocompatibility, and possible stimulus behavior via tunable structures. This review has gathered fundamental aspects of 3D/4D printing for biomaterials, and it shows the advances and applications of block copolymers in the field of biomaterials over the last years.