Development of a Graphene-Oxide-Deposited Carbon Electrode for the Rapid and Low-Level Detection of Fentanyl and Derivatives

Abstract

The opioid overdose crisis in North America worsened during the COVID-19 pandemic, with multiple jurisdictions reporting more deaths per day due to the fentanyl-contaminated drug supply than COVID-19. The rapid quantitative detection of fentanyl in the illicit opioid drug supply or in bodily fluids at biologically relevant concentrations (i.e., <80 nM) remains a significant challenge. Electroanalytical techniques are inexpensive and can be used to rapidly detect fentanyl, but detection limits need to be improved. Herein, we detail the development of an electrochemical-based fentanyl analytical detection strategy that used a glassy carbon electrode modified with electrochemically reduced graphene oxide (ERGO) via electrophoretic deposition. The resulting surface was further electrochemically reduced in the presence of fentanyl to enhance the sensitivity. Multiple ERGO thicknesses were prepared in order to prove the versatility and ability to fine-tune the layer to the desired response. Fentanyl was detected at <10 ppb (<30 nM) with a limit of detection of 2 ppb and a calibration curve that covered 4 orders of concentration (from 1 ppb to 10 ppm). This method was sensitive to fentanyl analogues such as carfentanil. Interference from the presence of 100-fold excess of other opioids (heroin, cocaine) or substances typically found in illicit drug samples (e.g. caffeine and sucrose) was not significant.

Electrochemical Determination of Fentanyl Using Carbon Nanofiber-Modified Electrodes

“…The redox pair OX3 and R2 is ascribed to the electrochemical redox behavior of norfentanyl on the fCNF/SPCE surface as has been established by others. 19 , 20 , 26 (We also conducted an independent CV experiment using our fCNF/SPCE in norfentanyl solution and observed redox pairs at the same potentials; see Supporting Information Figure S2a,b ). Phenylacetaldehyde, on the other hand, is not electroactive on the fCNF/SPCE ( Supporting Information Figures S2c,d ), and to the best of our knowledge, no literature report shows that it can be electrochemically oxidized or reduced.…”

“…In recent years, a number of reports have described electrochemical measurements of fentanyl, the majority of which are based on carbon electrodes such as carbon nano-onions, carbon nanotubes (CNTs), − carbon paste microneedles, screen-printed carbon electrodes (SPCEs), laser-ablated porous carbon electrodes, and graphene oxide-modified electrodes . Recent review articles on electrochemical sensors for fentanyl detection underscored the need for not only higher-performance devices capable of detecting extremely low concentrations (<80 nM) of fentanyl in both street drugs and in biologically relevant solutions but also the development of low-cost disposable sensors. , The above-cited literature establishes that the oxidation of the drug is adsorption-driven, − which can potentially create fouling effects from byproducts and other interferents present in fentanyl-containing samples. When this cross-contamination is an expected issue, the use of low-cost, disposable materials in sensor fabrication is advantageous.…”

“… 26 Recent review articles on electrochemical sensors for fentanyl detection underscored the need for not only higher-performance devices capable of detecting extremely low concentrations (<80 nM) of fentanyl in both street drugs and in biologically relevant solutions but also the development of low-cost disposable sensors. 27 , 28 The above-cited literature establishes that the oxidation of the drug is adsorption-driven, 19 − 26 which can potentially create fouling effects from byproducts and other interferents present in fentanyl-containing samples. When this cross-contamination is an expected issue, the use of low-cost, disposable materials in sensor fabrication is advantageous.…”

Postmortem toxicology findings from the Camden Opioid Research Initiative

“…The high incidence of caffeine, a stimulant also metabolized by cytochrome P450 enzymes, detected in 37 (88%) of the samples, may be due to commonly consumed caffeinated beverages, though there is literature to support that caffeine is introduced into the illicit opioid supply in an effort to make the drug less lethal in addition to simply adding bulk for increased profit [34][35][36][37]. Accounting for caffeine among the stimulants, all 42 (100%) of the cases showed evidence of co-occurring stimulant and opioid use.…”

Drogas emergentes: detección mediante sensores electroquímicos

“…DPV GC/CNOs PB pH 7,0 0,101 01-2020 [132] DPV Reticulado de SWCNT PBS pH 7,4 0,004 01-2020 [133] DPV Zn(II)-MOF/SP-C PB pH 7,0 0,101 04-2020 [134] AdSSWV SP-C Tris-HCl pH 8,5 0,233 0,037 07-2020 [135] AdSDPV MWCNT-GC PB pH 7,4 0,034 09-2020 [136] DPV NiO@CNTs/GC PBS pH 7,0 0,003 10-2021 [137] SWV LCE PBS pH 7,4 0,336 04-2022 [138] DPV GC/MWCNT-HA/Cu-H 3 BTC PBS pH 7,0 0,001 07-2022 [112] SWV Au sobre sustrato de MPSi/FEN-Ab PB pH 7,4 0,006 08-2022 [139] SWV ERGO-GC PBS pH 7,4 0,002 09-2022 [140] AdSCV Cytc/MWCNT/SP-C PB pH 7,5 0,086 11-2022 [141] Tabla 1. Sensores electroquímicos reportados en la literatura para la cuantificación de un grupo de NSP sintéticas.…”