Analytical determination of heroin, fentanyl and fentalogues using high-performance liquid chromatography with diode array and amperometric detection

Abstract

Over recent years there has been a progressive increase in the adulteration of common illicit street drugs, such as heroin and cocaine, with fentanyl and its derivatives (fentalogues) being the cause of over doses ending with fatal repercussions. Consequently, there is a need for the development of sensitive, selective and reliable analytical protocols for their separation and quantification. Herein, we report for the first time, a combination of high-performance liquid chromatography with a dual-diode array and electrochemical (amperometric) detector achieved for the simultaneous detection and quantification of heroin (HRN), fentanyl and ten fentalogues; the amperometric detection is achieved using a commercially available impinging jet flow-cell that incorporates in-house screen-printed graphite macroelectrodes (SPEs). Both protocols are analytically compared and contrasted in terms of their experimental parameters and chromatographic conditions with the separation and quantification being optimized, with these protocols demonstrating a high sensitivity and reproducibility. The proposed methods were successfully applied for the analysis of the investigated drugs of abuse, in the presence of common adulterants (e.g. caffeine, paracetamol and benzocaine), co-formulated excipients (starch, lactose, aerosil 200, etc.) and simultaneously within seized street samples. Scheme 1 Chemical synthesis and structures of fentanyl (2c), fentalogues (2a, 2b, 2d-2k), heroin (HRN) and cocaine (COC). a Mean AE SD of obtained % w/w of three determinations of each detected drug in each street sample. b Percentage relative standard deviation of obtained % w/w of three determinations of each detected drug in each street sample. c n.d. ¼ not detected.This journal is

Hyperpolarization of Pyridyl Fentalogues by Signal Amplification By Reversible Exchange (SABRE)

“…LC‐MS/MS (Liquid Chromatography‐Mass Spectrometry/ Mass Spectrometry) has been utilized to detect 24 fentanyl derivatives and metabolites in whole blood in under 14 min screening time . In addition, a dual HPLC‐DAD (High‐Performance Liquid Chromatography Diode‐Array Detector) and HPLC‐AD (Amperometric Detection) protocol that uses screen‐printed graphite macroelectrodes for amperometric detection has been developed for the simultaneous detection of 1 , 2 c and ten fentalogues . Furthermore, low‐field (62 MHz) NMR spectroscopy has been used to differentiate 65 fentalogues in conjunction with quantum mechanical spin system analysis of spectra acquired at a frequency of 600 MHz to produce comparison spectra .…”

An Overview of Recent Electroanalytical Applications Utilizing Screen‐Printed Electrodes Within Flow Systems

“…This approach was successfully applied for simultaneous analysis of investigational drugs of abuse in seized street samples in the presence of common adulterants (e. g. caffeine, paracetamol and benzocaine) and co-formulated excipients (starch, lactose, etc.). [108] A summary (analyte, sample, type of working electrode, LOD, and analytical frequency) on applications of SPEs coupled to HPLC systems are overviewed in Table 3.…”

Hitting the Jackpot – development of gas chromatography–mass spectrometry (GC–MS) and other rapid screening methods for the analysis of 18 fentanyl‐derived synthetic opioids

“…Sisco et al have reported a very sensitive direct analysis in real‐time mass spectrometry [DART‐MS, limit of detection = 0.08–0.35 ng] and ion mobility spectrometry [IMS, limit of detection = 1.0–10.0 ng] screening methods, but neither of these techniques facilitated efficient separation of the 18 analogs within the study . High performance liquid chromatography (HPLC) has been applied in a number of studies including one validated method, which has been developed and utilized to quantify ( 2b ) within bulk forensic samples of heroin . Hyphenated techniques (LC–MS, LC‐MS 2 and UPLC‐MS 2 ) have also been applied to detect fentalogs and their metabolites in blood, urine and wastewater .…”