The emergence of new psychoactive drugs in the market demands rapid and accurate tools for the on‐site classification of illegal and legal compounds with similar structures. Herein, a novel method for the classification of synthetic cathinones (SCs) is presented based on their electrochemical profile. First, the electrochemical profile of five common SC (i.e., mephedrone, ethcathinone, methylone, butylone, and 4‐chloro‐alpha‐pyrrolidinovalerophenone) is collected to build calibration curves using square wave voltammetry on graphite screen‐printed electrodes (SPEs). Second, the elucidation of the oxidation pathways, obtained by liquid chromatography–high‐resolution mass spectrometry, allows the pairing of the oxidation products to the SC electrochemical profile, providing a selective and robust classification. Additionally, the effect of common adulterants and illicit drugs on the electrochemical profile of the SC is explored. Interestingly, a cathodic pretreatment of the SPE allows the selective detection of each SC in presence of electroactive adulterants. Finally, the electrochemical approach is validated with gas chromatography–mass spectrometry by analyzing 26 confiscated samples from seizures and illegal webshops. Overall, the electrochemical method exhibits a successful classification of SC including structural derivatives, a crucial attribute in an ever‐diversifying drug market.
Herein, a straightforward electrochemical approach for the determination of ketamine in street samples and seizures is presented by employing screen-printed electrodes (SPE). Square wave voltammetry (SWV) is used to study the electrochemical behavior of the illicit drug, thus profiling the different oxidation states of the substance at different pHs. Besides, the oxidation pathway of ketamine on SPE is investigated for the first time with liquid chromatography−high-resolution mass spectrometry. Under the optimized conditions, the calibration curve of ketamine at buffer solution (pH 12) exhibits a sensitivity of 8.2 μA μM −1 , a linear relationship between 50 and 2500 μM with excellent reproducibility (RSD = 2.2%, at 500 μM, n = 7), and a limit of detection (LOD) of 11.7 μM. Subsequently, binary mixtures of ketamine with adulterants and illicit drugs are analyzed with SWV to investigate the electrochemical fingerprint. Moreover, the profile overlapping between different substances is addressed by the introduction of an electrode pretreatment and the integration of a tailor-made script for data treatment. Finally, the approach is tested on street samples from forensic seizures. Overall, this system allows for the on-site identification of ketamine by law enforcement agents in an easy-to-use and rapid manner on cargos and seizures, thereby disrupting the distribution channel and avoiding the illicit drug reaching the end-user.
Electrochemical strategies to selectively detect heroin in street samples without the use of complicated electrode modifications were developed for the first time. For this purpose, heroin, mixing agents (adulterants, cutting agent and impurities) and their binary mixtures were subjected to square wave voltammetry measurements at bare graphite electrodes at pH 7.0 and pH 12.0, in order to elucidate the unique electrochemical fingerprint of heroin and mixing agents as well as possible interferences or reciprocal influences. Adjusting the pH from pH 7.0 to pH 12.0 allowed a more accurate detection of heroin in the presence of most common mixing agents. Furthermore, the benefit of introducing a preconditioning step prior to running square wave voltammetry on the electrochemical fingerprint enrichment was explored. Mixtures of heroin with other drugs (cocaine, 3,4-methylenedioxymethamphetamine and morphine) were also tested to explore the possibility of their discrimination and simultaneous detection. The feasibility of the proposed electrochemical strategies was tested on realistic heroin street samples from forensic cases, showing promising results for fast, on-site detection tools of drugs of abuse.
This work describes a local induced near‐surface pH effect (pHS) arising from the presence of one analyte, leading to an influence or even suppression of redox signals of a second analyte present in solution. This concept and its impact on voltammetric sensing is illustrated by focusing on the detection of cocaine in the presence of the common adulterant benzocaine. An in‐depth study on the observed interference mechanism and its specificity for benzocaine and not for other adulterants was performed through the use of multiple electrochemical strategies. It was concluded that the potential shift and loss of intensity of the square‐wave voltammetric cocaine signal in the presence of benzocaine was caused by a local pHS effect. A cathodic pretreatment strategy was developed to nonetheless allow accurate cocaine detection. These insights are useful for explaining unidentified phenomena involving compounds with properties similar to benzocaine in voltammetric electroanalysis.
ReferencesAggregation of 'crowned' phthalocyanines by metal salts increases the electrical conductivity compared to the non-aggregated phthalocyanines. In a previous paper we described the synthesis and aggregation behaviour of phthalocyanines which contain crown ether subunits, e.g. (I).4 Compound (1) forms aggreg ates in the presence of alkali metal ions5 (Figure 1). We now report that these aggregates exhibit increased electrical conductivity as compared to uncomplexed (1) and unsubsti tuted phthalocyanines.K +, R b+, and Cs+ picrate complexes of (1) were prepared by mixing the latter compound and the appropriate metal picrate in a 1:4 ratio in chloroform-methanol (1:1 v/v) and stirring at -40 °C for two days. The gre£n precipitates were isolated by filtration, washed with hot methanol and chloro form until a colourless filtrate was obtained, and dried t Present address:
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