Critical to the success of three-dimensional (3D) printing of living materials with high performance is the development of new ink materials and 3D geometries that favor long-term cell functionality. Here we report the use of freeze-dried live cells as the solid filler to enable a new living material system for direct ink writing of catalytically active microorganisms with tunable densities and various self-supporting porous 3D geometries. Baker’s yeast was used as an exemplary live whole-cell biocatalyst, and the printed structures displayed high resolution, large scale, high catalytic activity and long-term viability. An unprecedented high cell loading was achieved, and cell inks showed unique thixotropic behavior. In the presence of glucose, printed bio-scaffolds exhibited increased ethanol production compared to bulk counterparts, due largely to improved mass transfer through engineered porous structures. The new living materials developed in this work could serve as a versatile platform for process intensification of an array of bioconversion processes utilizing diverse microbial biocatalysts for production of high-value products or bioremediation applications.

Recent advances in additive manufacturing, specifically direct ink writing (DIW) and ink-jetting, have enabled the production of elastomeric silicone parts with deterministic control over the structure, shape, and mechanical properties. These new technologies offer rapid prototyping advantages and find applications in various fields, including biomedical devices, prosthetics, metamaterials, and soft robotics. Stereolithography (SLA) is a complementary approach with the ability to print with finer features and potentially higher throughput. However, all high-performance silicone elastomers are composites of polysiloxane networks reinforced with particulate filler, and consequently, silicone resins tend to have high viscosities (gel- or paste-like), which complicates or completely inhibits the layer-by-layer recoating process central to most SLA technologies. Herein, the design and build of a digital light projection SLA printer suitable for handling high-viscosity resins is demonstrated. Further, a series of UV-curable silicone resins with thiol-ene crosslinking and reinforced by a combination of fumed silica and MQ resins are also described. The resulting silicone elastomers are shown to have tunable mechanical properties, with 100–350% elongation and ultimate tensile strength from 1 to 2.5 MPa. Three-dimensional printed features of 0.4 mm were achieved, and complexity is demonstrated by octet-truss lattices that display negative stiffness.

Polysiloxane elastomers have a large application space due to their versatile cross-linking chemistry and highly tunable physical and mechanical properties. One approach for improving the mechanical integrity of commercial polysiloxane “silicone” elastomers while maintaining their optical transparency is the addition of small, silicone-resin molecules to the network. However, both the poly(dimethylsiloxane) (PDMS) network and the silicone-resin particles have an amorphous structure and complex chemistry, which makes the characterization of their structural properties and segmental network dynamics difficult. Here, we report the synthesis and characterization of a series of model silicone networks modified with a specific class of silicone-resin known as MQ-resin using Raman and advanced nuclear magnetic resonance (NMR) spectroscopy methods. Raman spectroscopy was successfully used to quantify the contribution of the MQ-resin to the network, to determine the type of MQ-resin present in the network, and to investigate the completeness of the network cross-linking reaction. Solid-state and ¹H double-quantum (DQ) NMR spectroscopies were used not only as a detection method for the MQ-resins but also to quantify changes in the segmental dynamics of the network as a function of MQ-resin concentration. The combination of Raman and NMR spectroscopies describes a series of samples where the MQ-resin particles and PDMS chains maintain their independent segmental dynamics up to high concentrations of MQ-resins (40–50% MQ), where the physical properties of the resin dominate the physical properties of the overall network. The results from our spectroscopic analyses are consistent with the results from macroscopic characterization techniques such as solvent uptake and mechanical testing. The spectroscopic insights into the structure–property relationships of PDMS-MQ composites presented in this study are a valuable tool not only for the synthesis and reverse engineering of future generations of commercial silicone elastomers but also for understanding the mechanisms of aging and degradation over the material lifetime.