Molecular Information Processing in a Chemical Reaction Network Using Surface-Mediated Polyelectrolyte Complexation

Biochemical communication is ubiquitous in life. Biology uses chemical reaction networks to regulate concentrations of myriad signaling molecules. Recent advances in supramolecular and systems chemistry demonstrate that feedback mechanisms of such networks can be rationally designed but strategies to transmit and process information encoded in molecules are still in their infancy. Here, we designed a polyelectrolyte reaction network maintained under out-of-equilibrium conditions using pH gradients in flow. The network comprises two weak polyelectrolytes (polyallylamine, PAH, and polyacrylic acid, PAA) in solution and one immobilized on the surface (poly-l-lysine, PLL). We chose PAH and PAA as their complexation process is known to be history-dependent (i. e., the preceding state of the system can determine the next state). Surprisingly, we found that the hysteresis diminished as the PLL-coated surface supported rather than perturbed the formation of the complex. PLL-coated surfaces are further exploited to establish that reversible switching between the assembled and disassembled state of polyelectrolytes can process signals encoded in the frequency and duration of pH pulses. We envision that the strategy employed to modulate information in this polyelectrolyte reaction network could open novel routes to transmit and process molecular information in biologically relevant processes. This work reports the design of a polyelectrolyte-based reaction network. The network is maintained under out-of-equilibrium conditions using a microfluidic channel. Immobilization of one of the polyelectrolytes in the channel provides control over state of the system, i. e., disassembled (polyelectrolytes) and assembled (polyelectrolyte complex). The strategy employed allows for signal modulation encoded in the frequency and duration of pH pulses. image