Spatiotemporal Control of Enzyme-Induced Crystallization Under Lyotropic Liquid Crystal Nanoconfinement.

Water nanoconfinement has important effects on the properties of biomolecules and ultimately on their specific functions. By performing experiments and molecular dynamic simulations, we show how intrinsic nanoconfinement controls the crystallization of small organic molecules converted by enzymatic reactions within the water nanochannels of lipid cubic phases (LCPs). By controlling the nanochannel size, enzymatic reactions in LCPs can be engineered to turn the same converted substrate into its soluble, microcrystal, or needle-like crystal form due to the large variability in water dynamics. Differential scanning calorimetry studies, supported by molecular dynamics simulations, show that most of water within the mesophase nanochannels behaves differently due to interactions with the LCP interface, and that this mechanism has a larger impact for smaller channels. These findings suggest that the amount of free water in the core of the nanochannels is the key factor determining local substrate diffusion and self-assembly within LCPs.