Applications of cryostructures in the chromatographic separation of biomacromolecules

•Supermacroporous cryostructures are prepared via a cryoprocess approach.•Cryostructures are used as stationary phases for separating biomacromolecules.•Cryostructures have high surface area and low-pressure drop.•Proteins, antibodies, and DNA can be separated using cryostructures.•Separated biomacromolecules retain their properties following separation. Macroporous-interconnected cryostructures are prepared via cryoprocess approaches, where polymerization, crosslinking-polymerization, or even chain aggregation is primarily conducted at the sub-freezing temperature of the medium followed by thawing. Given their unique desirable properties, cryostructures have been studied as a stationary phase in chromatography to purify and separate proteins. The macroporous cryostructures with their highly interconnected large (10–100 µm) pores have various advantages, including the high surface area, sponge-like morphology, high elasticity, low-pressure drop, short diffusion path, and a temporary residence. In this review, we elaborate on the methods used in the preparation of cryostructures and the factors affecting their properties. We also highlight the underlying progress in chromatography techniques that take advantage of cryostructures as stationary phases for separating multiple biomacromolecules.