Abstract3D printing offers enormous flexibility in fabrication of polymer objects with complex geometries. However, it is not suitable for fabricating large polymer structures with geometrical features at the sub-micrometer scale. Porous structure at the sub-micrometer scale can render macroscopic objects with unique properties, including similarities with biological interfaces, permeability and extremely large surface area, imperative inter alia for adsorption, separation, sensing or biomedical applications. Here, we introduce a method combining advantages of 3D printing via digital light processing and polymerization-induced phase separation, which enables formation of 3D polymer structures of digitally defined macroscopic geometry with controllable inherent porosity at the sub-micrometer scale. We demonstrate the possibility to create 3D polymer structures of highly complex geometries and spatially controlled pore sizes from 10 nm to 1000 µm. Produced hierarchical polymers combining nanoporosity with micrometer-sized pores demonstrate improved adsorption performance due to better pore accessibility and favored cell adhesion and growth for 3D cell culture due to surface porosity. This method extends the scope of applications of 3D printing to hierarchical inherently porous 3D objects combining structural features ranging from 10 nm up to cm, making them available for a wide variety of applications.

Cell adhesive and other functional peptides (such as RGD, KRSR, YIGSR, VAPG, and BMP-2 peptides) are extensively studied and utilized in tissue engineering scaffolds and biomedical devices to modulate cell functions. Though PEG is frequently used as the antifouling layer, it is unclear how it affects the performance of functional peptides. By analyzing the impact of PEG at short (OEG4), medium (OEG8), and long chain length (PEG2K), we reveal that PEG chain length is critical and a medium-length PEG enables functional peptides to display their optimal and genuine functions in cell adhesion, migration, and differentiation by providing excellent antifouling to minimize background noise of unwanted cell adhesion and high enough surface density of functional peptides. Our result provides new avenues for maximizing the genuine functions of peptides. This study also provides a solution to prevent the heterogeneous and even divergent results caused by inappropriate choice of antifouling PEG and provides a general guidance in identifying new functional peptides.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201806733.Polymeric porous media (PPM) are widely used as advanced materials, such as sound dampening foams, lithium-ion batteries, stretchable sensors, and biofilters. The functionality, reliability, and durability of these materials have a strong dependence on the microstructural patterns of PPM. One underlying mechanism for the formation of porosity in PPM is phase separation, which engenders polymer-rich and polymer-poor (pore) phases. Herein, the phase separation in polymer solutions is discussed from two different aspects: diffusion and hydrodynamic effects. For phase separation governed by diffusion, two novel morphological transitions are reviewed: "cluster-topercolation" and "percolation-to-droplets," which are attributed to an effect that the polymer-rich and the solvent-rich phases reach the equilibrium states asynchronously. In the case dictated by hydrodynamics, a deterministic nature for the microstructural evolution during phase separation is scrutinized. The deterministic nature is caused by an interfacial-tensiongradient (solutal Marangoni force), which can lead to directional movement of droplets as well as hydrodynamic instabilities during phase separation. Polymeric Porous Media