3D Printing of Bioinspired Alginate‐Albumin Based Instant Gel Ink with Electroconductivity and Its Expansion to Direct Four‐Axis Printing of Hollow Porous Tubular Constructs without Supporting Materials

Abstract A successful 3D printable hydrogel ink needs not only biofunctionalities but also minimal fabrication steps such as multiple crosslinking sites, high printability, cytocompatibility, high shape fidelity, stability, shear thinning, robust properties, and less time‐consuming processing steps, by maximizing known material chemistries and functionalities. This work reports a novel bioinspired conjugate with polysaccharide (alginate)–tannic acid (TA)–protein (bovine serum albumin) to fabricate proteoglycan‐like gels, which are 3D printable with multilayers, shear‐thinning, elastic, electroconductive (with carbon nanotubes), controlled crosslinking/degradation through multiple crosslinking mechanisms (TA, Ca²⁺ ions, and NaIO₄ oxidation), and interactions with cytocompatible hydrogel system. The synthesis process is simple, and gelation (within 2 h) is ensured without any chemical crosslinking agents (at room temperature). While cell‐adhesive albumin largely improves cytocompatibility, carbon nanotubes in the gel give electrical conductivity in the different four‐axis 3D printed structures, including large hollow tubular constructs. This work demonstrates promising results of electroconductive proteoglycan‐like gel ink to address the challenges in 3D/four‐axis ink printing such as synthesis, printability, shape fidelity, electroconductivity, controlled fabrication and degradation, cytocompatibility, and multiple crosslinking abilities to maintain the dimensions of the diversely printed constructs.