Integrating Pore Architectures to Evaluate Vascularization Efficacy in Silicate-based Bioceramic Scaffolds

Pore architecture in bioceramic scaffolds plays an important role in facilitating vascularization efficiency during bone repair or orbital reconstruction. Many investigations have explored this relationship but lack integrating pore architectural features in a scaffold, hindering optimization of architectural parameters (geometry, size, curvature) to improve vascularization and consequently clinical outcomes. To address this challenge, we have developed an integrating design strategy to fabricate different pore architectures (cube, gyroid, hexagon) with different pore dimensions (∼350, 500, 650 μm) in the silicate-based bioceramic scaffolds via digital light processing technique. The sintered scaffolds maintained high-fidelity pore architectures similar to the printing model. The hexagon- and gyroid-pore scaffolds exhibited the highest and lowest compressive strength (from 15 to 55 MPa), respectively, but the cube-pore scaffolds showed appreciable elastic modulus. Moreover, the gyroid pore architecture contributed on a faster ion dissolution and mass decay in vitro. It is interesting that both μCT and histological analyses indicate vascularization efficiency was challenged even in the 650-μm pore region of hexagon-pore scaffolds within 2 weeks in rabbit models, but the gyroid pore constructs indicated appreciable blood vessel networks even in the 350-μm pore region at 2 weeks and high-density blood vessels were uniformly invaded in the 500- and 650-μm pore at 4 weeks. Angiogenesis was facilitated in the cube-pore scaffolds in comparison with the hexagon-pore ones within 4 weeks. These studies demonstrate that the continuous pore wall curvature feature in gyroid pore architecture is an important implication for biodegradation, vascular cell migration and vessel ingrowth in porous bioceramic scaffolds.

Linking metal-organic cages pairwise as a design approach for assembling multivariate crystalline materials

Using metal-organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal-organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network via this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials. Our methodology exploits preferential Rh-aniline coordination and stoichiometric control to rationally link Cu4L4 and Rh4L4 MOCs into chemically complex, yet extremely well-defined crystalline solids. This strategy is expected to open up significant new possibilities to design bespoke multi-functional materials with atomistic control over the location and ordering of chemical functionalities.

Unidirectional ion transport in nanoporous carbon membranes with a hierarchical pore architecture

The transport of fluids in channels with diameter of 1-2 nm exhibits many anomalous features due to the interplay of several genuinely interfacial effects. Quasi-unidirectional ion transport, reminiscent of the behavior of membrane pores in biological cells, is one phenomenon that has attracted a lot of attention in recent years, e.g., for realizing diodes for ion-conduction based electronics. Although ion rectification has been demonstrated in many asymmetric artificial nanopores, it always fails in the high-concentration range, and operates in either acidic or alkaline electrolytes but never over the whole pH range. Here we report a hierarchical pore architecture carbon membrane with a pore size gradient from 60 nm to 1.4 nm, which enables high ionic rectification ratios up to 104 in different environments including high concentration neutral (3 M KCl), acidic (1 M HCl), and alkaline (1 M NaOH) electrolytes, resulting from the asymmetric energy barriers for ions transport in two directions. Additionally, light irradiation as an external energy source can reduce the energy barriers to promote ions transport bidirectionally. The anomalous ion transport together with the robust nanoporous carbon structure may find applications in membrane filtration, water desalination, and fuel cell membranes.