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

Overview

Journal ACS Mater Lett

Publisher American Chemical Society

Date 2024 Sep 23

PMID 39309214

Authors

Farbod Amirghasemi

Abdulrahman Al-Shami

Kara Ushijima

Maral P S Mousavi

Affiliations

Soon will be listed here.

Abstract

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.

References

Boswell P, Buhlmann P . Fluorous bulk membranes for potentiometric sensors with wide selectivity ranges: observation of exceptionally strong ion pair formation. J Am Chem Soc. 2005; 127(25):8958-9. DOI: 10.1021/ja052403a. View

Boswell P, Szijjarto C, Jurisch M, Gladysz J, Rabai J, Buhlmann P . Fluorophilic ionophores for potentiometric pH determinations with fluorous membranes of exceptional selectivity. Anal Chem. 2008; 80(6):2084-90. DOI: 10.1021/ac702161c. View

Johnson Z, Williams K, Chen B, Sheets R, Jared N, Li J . Electrochemical Sensing of Neonicotinoids Using Laser-Induced Graphene. ACS Sens. 2021; 6(8):3063-3071. DOI: 10.1021/acssensors.1c01082. View

Chen B, Johnson Z, Sanborn D, Hjort R, Garland N, Soares R . Tuning the Structure, Conductivity, and Wettability of Laser-Induced Graphene for Multiplexed Open Microfluidic Environmental Biosensing and Energy Storage Devices. ACS Nano. 2021; 16(1):15-28. DOI: 10.1021/acsnano.1c04197. View

Ruiz-Cabello J, Walczak P, Kedziorek D, Chacko V, Schmieder A, Wickline S . In vivo "hot spot" MR imaging of neural stem cells using fluorinated nanoparticles. Magn Reson Med. 2008; 60(6):1506-11. PMC: 2597664. DOI: 10.1002/mrm.21783. View

Campoccia D, Montanaro L, Arciola C . A review of the biomaterials technologies for infection-resistant surfaces. Biomaterials. 2013; 34(34):8533-54. DOI: 10.1016/j.biomaterials.2013.07.089. View

Picciotto M, Higley M, Mineur Y . Acetylcholine as a neuromodulator: cholinergic signaling shapes nervous system function and behavior. Neuron. 2012; 76(1):116-29. PMC: 3466476. DOI: 10.1016/j.neuron.2012.08.036. View

Li Y, Luong D, Zhang J, Tarkunde Y, Kittrell C, Sargunaraj F . Laser-Induced Graphene in Controlled Atmospheres: From Superhydrophilic to Superhydrophobic Surfaces. Adv Mater. 2017; 29(27). DOI: 10.1002/adma.201700496. View

Boswell P, Lugert E, Rabai J, Amin E, Buhlmann P . Coordinative properties of highly fluorinated solvents with amino and ether groups. J Am Chem Soc. 2005; 127(48):16976-84. PMC: 2527468. DOI: 10.1021/ja055816k. View

10.

Sacramento A, Moreira F, Guerreiro J, Tavares A, Sales M . Novel biomimetic composite material for potentiometric screening of acetylcholine, a neurotransmitter in Alzheimer's disease. Mater Sci Eng C Mater Biol Appl. 2017; 79:541-549. DOI: 10.1016/j.msec.2017.05.098. View

11.

Chen L, Lai C, Granda L, Fierke M, Mandal D, Stein A . Fluorous membrane ion-selective electrodes for perfluorinated surfactants: trace-level detection and in situ monitoring of adsorption. Anal Chem. 2013; 85(15):7471-7. DOI: 10.1021/ac401424j. View

12.

Otte E, Vlachos A, Asplund M . Engineering strategies towards overcoming bleeding and glial scar formation around neural probes. Cell Tissue Res. 2022; 387(3):461-477. PMC: 8975777. DOI: 10.1007/s00441-021-03567-9. View

13.

Gunsolus I, Mousavi M, Hussein K, Buhlmann P, Haynes C . Effects of Humic and Fulvic Acids on Silver Nanoparticle Stability, Dissolution, and Toxicity. Environ Sci Technol. 2015; 49(13):8078-86. PMC: 4643692. DOI: 10.1021/acs.est.5b01496. View

14.

Bohnen N, Yarnall A, Weil R, Moro E, Moehle M, Borghammer P . Cholinergic system changes in Parkinson's disease: emerging therapeutic approaches. Lancet Neurol. 2022; 21(4):381-392. PMC: 8985079. DOI: 10.1016/S1474-4422(21)00377-X. View

15.

Wei Y, Li X, Wang Y, Hirtz T, Guo Z, Qiao Y . Graphene-Based Multifunctional Textile for Sensing and Actuating. ACS Nano. 2021; 15(11):17738-17747. DOI: 10.1021/acsnano.1c05701. View

16.

Patrick M, Janjic J, Teng H, OHear M, Brown C, Stokum J . Intracellular pH measurements using perfluorocarbon nanoemulsions. J Am Chem Soc. 2013; 135(49):18445-57. PMC: 4208472. DOI: 10.1021/ja407573m. View

17.

Chen X, Mousavi M, Buhlmann P . Fluorous-Phase Ion-Selective pH Electrodes: Electrode Body and Ionophore Optimization for Measurements in the Physiological pH Range. ACS Omega. 2020; 5(23):13621-13629. PMC: 7301372. DOI: 10.1021/acsomega.0c00582. View

18.

Yang W, Zhao W, Li Q, Li H, Wang Y, Li Y . Fabrication of Smart Components by 3D Printing and Laser-Scribing Technologies. ACS Appl Mater Interfaces. 2020; 12(3):3928-3935. DOI: 10.1021/acsami.9b17467. View

19.

Mousavi M, Abd El-Rahman M, Mahmoud A, Abdelsalam R, Buhlmann P . In Situ Sensing of the Neurotransmitter Acetylcholine in a Dynamic Range of 1 nM to 1 mM. ACS Sens. 2018; 3(12):2581-2589. DOI: 10.1021/acssensors.8b00950. View

20.

Buhlmann P, Pretsch E, Bakker E . Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 2. Ionophores for Potentiometric and Optical Sensors. Chem Rev. 2002; 98(4):1593-1688. DOI: 10.1021/cr970113+. View