<p>Hierarchical molecular assembly directed by cell-regulated
aqueous solvent is a fundamental strategy for manufacturing various proteinaceous
structures that are of intense interest for nanotechnology, sustainable
manufacturing and regenerative medicine. However, to translate the natural
strategy into advanced digital manufacturing like three-dimensional (3D)
printing remains a tremendous technical and theoretical challenge. This work
presents a 3D printing technique of a particular protein, silk fibroin, by
rationally designing an<i> de novo </i>aqueous
salt bath capable of directing the hierarchical assembly of the protein
molecules. This technique, conducted under aqueous and ambient conditions,
results in 3D proteinaceous architectures characterized by intrinsic
biocompatibility/biodegradability and remarkable mechanical performance. The
versatility of this method is shown in a diversity of 3D shapes and a range of functional
components integrated into the 3D prints. Exceptional manufacturing capability
and one promising application is exemplified by the single-step construction of
perfusable microfluidic chips, also an analogy of small-diameter vascular grafts,
which eliminates the use of supporting or sacrificial materials owing to optimized
crosslinking dynamics and compartmentalized printing parameters. The 3D shaping
capability of the protein material can benefit a multitude of biomedical devices,
from drug delivery to surgical implants to tissue scaffolds.</p>