Enzyme Kinetics in Liquid Crystalline Mesophases: Size Matters, But Also Topology

Lyotropic liquid crystalline systems (LLCs) are excellent immobilizing carriers for enzymes, due to their biocompatibility and well-defined pore nanostructure. Here we show that the liquid crystalline mesophase topology can greatly influence the enzymatic activity in a typical peroxidase (Horseradish peroxidase, HRP) enzymatic reaction. Enzyme kinetics was investigated in different LLC mesophases based on monolinolein, with varying symmetries and dimensions such as the 1D cylindrical inverse hexagonal phase (HII), the 2D planar lamellar phase (Lα), and two 3D bicontinuous cubic phases of double diamond (Pn3m) and gyroid (Ia3d) space groups. As expected, the mesophase with largest water channel size shows highest activity, regardless of the topology. Interestingly, however, when mesophases with different topologies have the same water channel size, then the topology plays the dominant role, and the enzyme showed the highest activity in the 3D tetra-fold connected Pn3m, followed by the Ia3d with trifold connectivity, and finally the 1D HII phase. This study demonstrates that the enzymatic activity in LLC mesophases depends on both the water channel size and the topology of the mesophase.