Flexible Acetylcholine Neural Probe with a Hydrophobic Laser-Induced Graphene Electrode and a Fluorous-Phase Sensing Membrane.

This work develops the first laser-induced graphene (LIG)-based electrochemical sensor with a superhydrophobic fluorous membrane for a flexible acetylcholine (ACh) sensor. ACh regulates several physiological functions, including synaptic transmission and glandular secretion. The ACh sensing membrane is doped with a fluorophilic cation-exchanger that can selectively measure ACh based on the inherent selectivity of the fluorous phase for hydrophobic ions, such as ACh. The fluorous-phase sensor improves the selectivity for ACh over Na and K by 2 orders of magnitude (compared to traditional lipophilic membranes), thus lowering the detection limit in artificial cerebrospinal fluid (aCSF) from 331 to 0.38 M, thereby allowing measurement in physiologically relevant ranges of ACh. Engraving LIG under argon creates a hydrophobic surface with a 133.7° contact angle, which minimizes the formation of a water layer. The flexible solid-contact LIG fluorous sensor exhibited a slope of 59.3 mV/decade in aCSF and retained function after 20 bending cycles, thereby paving the way for studying ACh's role in memory and neurodegenerative diseases.