To understand the importance of water in biomacromolecules and supramolecular materials, the monodispersed 1 nm porous organic nanocage (POC) is studied for their hierarchical condensed structures and relaxation dynamics at different hydration levels. The POCs possess flexible framework and their bulks stay intrinsically in glassy state with well-defined transition temperatures (T_g) and they can be attenuated from 61 to −50 °C with glass-to-rubber transition upon the increasing of hydration levels. Two-level relaxation dynamics can be probed and the temperature dependence of their relaxation time differentiates them as cooperative backbone dynamics (α) and local groups dynamics (β). The dynamical transition of α relaxation is consistent with T_g in hydration dependence. Suggested from MD simulation, water binds to the surface amine groups of POCs and accelerate its local dynamics, leading to the activated backbone dynamics for the broadly tunable visco-elasticity and thermal hysteresis for anti-freeze property. In small-angle X-ray scattering studies, the physical denaturation of POC can be observed as collapsed molecular framework and altered solubility when heated above their T_g in salt solutions. The microscopic understanding inspires the applications of hydrated POCs for elastomers and aqueous lithium electrolyte with high ionic conductivity, chemical stability and mechanical flexibility.

Long-lasting protective immune responses are expected following vaccination. However, most vaccines alone are inability to evoke an efficient protection. The combinatory administration of adjuvants with vaccines is critical for generating the enhanced immune responses. Herein, with biocompatible poly(4-vinylpyridine) (P4VP) as template, 2.5 nm iron/molybdenum oxide cluster, {Mo₇₂Fe₃₀}, is applied as an adjuvant to co-assemble with antigens of Mycobacterium bovis via hydrogen bonding at molecular scale. Molecular scale integration of the antigens and {Mo₇₂Fe₃₀} and their full exposure to body fluid media contribute to the augmentation of both humoral and cellular immune responses of the vaccines after inoculation in mice. Anti-inflammatory factor IL-10 gradually increases after 2 weeks followed by a final back to normal level by the 5th week. The balance between proinflammatory cytokines and anti-inflammatory factors suggests that immune system can be activated in the early stage of infection by the antigens carried by the supra-particles and secrete acute inflammatory factors for host defense and anti-inflammatory factors for immune protection.