mats de Jong ac, Nick Sleegers a, Jayoung Kim b, Filip valve Durme c, Nele Samyn c, Joseph Wang b and also Karolien De Wael *a aAXES research study Group, Chemistry Department, Groenenborgerlaan 171, 2020 Antwerp, Belgium. E-mail: karolien.dewael bDepartment the Nanoengineering, university California mountain Diego, CA 92093, USA cNational Institute for Criminalistics and also Criminology (NICC), Vilvoordsesteenweg 100, 1120 Brussels, Belgium


We report ~ above a wearable fingertip sensor because that on-the-spot identification of cocaine and also its cutting agents in street samples. Traditionally, on-site screening is performed by means of color tests i beg your pardon are an overwhelming to interpret and lack selectivity. By presenting the unique voltammetric response of cocaine, cut agents, binary mixture of cocaine and street samples in solution and also powder street samples, we were able to elucidate the electrochemical fingerprint of every these compounds. The brand-new electrochemical ide holds significant promise together an on-site screening method.

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Cocaine is among the many abundant drugs of abuse worldwide, entering different countries mainly via airports and harbours, both for regional consumption and for distribution.1 This alkaloid medicine is very addictive and harmful because that people"s health.2,3 In enhancement to the desired effects for customers such as an intense euphoric feeling, undesirable second effects prefer an enhanced blood pressure, heartbeat rate and also respiration rate are experienced.4,5 After long-term use, the addict i do not care tolerant because that the desired effects and also will endure a state that lethargy, major depression and extreme fatigue when no longer using cocaine.4

Customs services at airports and harbours are an extremely keen to screen passing cargo, luggage and also people because that the existence of cocaine. On-site screening by way of colour tests based upon cobalt thiocyanate is typically performed. However, this tests are daunting to interpret and not constantly reliable since of a bad selectivity.6,7 normally the colour exam are complied with by a confirmation analysis by way of GC-MS (qualitative), GC-FID (quantitative) and also HPLC for an unambiguous identification of cocaine and also its cutting agents. This confirmation supplies a range of laborious and complicated techniques and/or bulky and also expensive tools that should be avoided for program screenings.8 An different screening have the right to be performed by FT-IR and also Raman spectroscopy, using expensive instrumentation providing spectra the are challenging to interpret without dedicated expertise.9 To overcome these limitations, the present study intends at a fast, cheap, easy, and selective screening test because that on-site detection the cocaine.

Knowing that cocaine is a redox energetic molecule,10 one electrochemical screening method by record voltammograms allows customs come quickly screen unknown flour in cargo and also baggage on-site, facilitating high throughput and also low expense of detection. Even more, most cutting agents have the right to be sensed in addition to cocaine because of their redox activity.11–18 this cutting agents are added to cocaine by the dealers, mainly in order to maximise profit. Usual substances space phenacetin, caffeine, levamisole, lidocaine, paracetamol, procaine, benzocaine, diltiazem, hydroxyzine, boric and also benzoic acid, and several sugars choose D-sorbitol, myo-inositol, maltose and starch. This compounds all have actually a white colour choose cocaine and also some the them, for instance lidocaine, paracetamol and also phenacetin, have analgesic and anesthetic effects the customers will relate to cocaine.17,18 Voltammograms save much much more information because that identification of street samples comprise both cocaine and cutting agents compared to the traditional colour tests that rely specifically on the visibility of cocaine. Below we define the usefulness that electrochemical methods to measure concurrently cocaine and also its cut agents in a solitary voltammetric operation via square-wave voltammetry (SWV). In bespeak to achieve the full and also distinct electrochemical fingerprint of street samples, all cutting agents and cocaine have actually been electrochemically screened individually in solution and in a binary mixture. Secondly, flour samples to be analysed by using the electrochemical approach, enabling a fast and easy on-site detection, without comprehensive sample preparation procedure. The sensing device being incorporated into a glove/fingertip, allows such on-site detection.19 The measuring protocol is gift in Fig. 1. Component (A) represents the finger exhibiting the three electrode surface screen-printed onto a functional finger cot (bottom left inset), and gel immobilized ~ above a similar substrate (bottom best inset). Part (B) and (C) illustrate, respectively, the ‘swipe’ technique of sampling to collect the target powder directly onto the electrode and also the completion of the electrochemical cabinet by involvement the index finger with electrodes come the ignorance coated with the hard hydrogel electrolyte. The electrochemical fingerprint is taped in less than a minute by utilizing a fast square-wave voltammetric approach, giving information on both the presence of cocaine and its cut agents.

Fig. 1 Schematic the the measure up procedure for suspicious powder samples at a wearable fingertip device. (A) The fingertip exhibiting the surface ar of screen-printed electrode top top a versatile nitrile finger cot (bottom left inset), and also a conductive gel immobilized ~ above the thumb (bottom right inset); (B) swiping an approach of sampling to collection the target powder directly onto the electrode; (C) completion of the electrochemical cabinet by authorized the table of contents finger v electrodes to the ignorance coated v the conductive gel electrolyte.

We mean that this brand-new electrochemical fingerprint on a wearable glove platform will considerably enhance the on-site screening that cocaine samples. The capability to rapidly generate this signature through a single scan method using compact, cheap and also easy-to-use electrochemical gadgets should be an extremely useful for on-site detection, performed by custom-mades services. For the an initial time, the existence of cut agents in street samples is elucidated in one on-site test.

Results and discussion

Voltammetry that pure link in solution

A an initial and an important step is the screening and also assessment the the oxidization behaviour of cocaine and also its cutting agents in solution to clear the electrochemical fingerprint of these compounds. Square-wave voltammograms that 1 mM cocaine or cutting agent in a 0.1 M KCl + 0.020 M KH2PO4 equipment at a ceiling carbon screen-printed electrode are shown in Fig. 2, corrected for the background current by utilizing the moving typical principle, combined in the NOVA 1.11 software. The 1 mM cocaine solution exhibits a weak oxidation procedure at 1.04 V which have the right to be added to the oxidation of the tertiary amine group existing in the hexagon structure of cocaine as is displayed in system 1.10 most cocaine samples are reduced with different substances; to know of this cutting agents could be of interest from a toxicological suggest of view. The parameters the the provided square-wave voltammetry procedure were optimized front the evaluation and are explained in the experimental part.
Fig. 2 Baseline-corrected square-wave voltammetric responses (vs. Ag/AgCl) of 1 mM options of cocaine and also cutting agents at bare carbon screen-printed electrodes in 0.1 M KCl + 0.020 M KH2PO4 buffer (pH 7). The dotted line represents the characteristic oxidation potential the cocaine in ~ 1.04 V. The y-axis has actually the very same scale in every voltammogram.

Scheme 1 Oxidation procedure of cocaine in ~ a carbon screen-printed electrode in ~ potential 1.04 V. The 2nd reaction occurs immediately after the formation of the intermediate radical, resulting in only one visible peak in a square-wave voltammogram.

Cutting agents benzoic acid and also boric acid show no redox task over the studied potential range, which coincides with the literature, only showing task at potentials below −1 V because that these compounds.14,15 The street D-sorbitol, maltose, starch and also myo-inositol also show no redox activity in the studied potential range. Fig. 2 illustrates the the cocaine signal in ~ 1.04 V is rather isolated indigenous the other characteristic signals of the cut agents. The closest more positive process is the height of levamisole at 1.27 V and the closest more negative is the peak of lidocaine at 0.90 V and its analogues procaine and also benzocaine, 0.87 V and also 0.84 V, respectively. All these oxidation processes occur at tertiary (levamisole and also lidocaine) and also primary (benzocaine and also procaine) amine useful groups.11,12,17,20 except these optimal potential values, the number of characteristic peaks and the beginning potentials give helpful information top top determining your fingerprint. Phenacetin, for instance, displays three critical redox processes, so also if over there is one overlap through the major oxidation peak, the present cutting agent can still be identified by its second or tertiary signal. The major signal at 0.77 V results from the irreversible oxidation of phenacetin come N-acetyl-p-benzoquinone imine (NAPQI). The smaller secondary peaks in ~ 0.06 and 0.35 V room a an outcome of the oxidation the 4-aminophenol and NAPQI, respectively.21 these two second peaks are likewise present for paracetamol and are caused by the very same compounds.18 Hydroxyzine and diltiazem both show an oxidation top at 0.87 V, resulted in by the oxidation the a totally free –OH group and a tertiary amine, respectively.16,22 Caffeine has actually the greatest oxidation potential at 1.31 V, result from the oxidation that the compound to a 4,5-diol analogue.13

This considerable screening and rich information content leads to a unique electrochemical fingerprint that cocaine and also its cut agents that deserve to serve as a powerful reference as soon as the presence of cocaine in one unknown sample requirements to be evidenced or ruled out.

The applied conditioning step at 1.5 V (as is defined in the speculative section) was performed to extract maximal information from ours substances. Because that instance, phenacetin would certainly only display a solitary peak in ~ 0.77 V rather of 3 peaks if no conditioning action was performed. As result of the conditioning step, redox procedures related to NAPQI and 4-aminophenol take place, enriching the fingerprint of the samples.

The limit of detection (LOD) because that pure cocaine ~ above the non-modified screen-printed electrode (SPE) surface ar in systems was established at 2 μM. This synchronizes to a quantity of 34 ng top top the electrode surface. The LOD to be determined based on the conventional deviation the the intercept and also the average slope that the direct calibration curves the were obtained.

This LOD is significantly lower contrasted to the color screening tests (13.8 μM) and the accredited GC-MS technique used at the national Institute that Criminalistics and also Criminology (NICC) of Belgium (18.4 μM).

Voltammetry of binary mixture in solution

critical second step is the assessment of the oxidization behaviour the cocaine and also the cutting agents in mixtures to elucidate potential masking (overlapping peak) phenomena.

Square-wave voltammograms that 1 mM cocaine and also 0.5 mM cut agent in a 0.1 M KCl + 0.020 M KH2PO4 solution (pH 7) in ~ a ceiling carbon screen-printed electrode are presented in Fig. 3.

Fig. 3 Baseline-corrected square-wave voltammetric responses (vs. Ag/AgCl) that 1 mM options of cocaine through 0.5 mM cutting agent at ceiling carbon screen-printed electrodes in 0.1 M KCl + 0.020 M KH2PO4 buffer (pH 7). The dotted heat represents the characteristic oxidation potential the cocaine at 1.04 V. The y-axis has the same scale in every voltammogram.

There are no far-reaching peak shifts visible for the cocaine signal and the cut agent peaks do happen at your characteristic potential values. This peak potential of the cocaine oxidation process is only slightly change in the existence of benzocaine, levamisole, caffeine, phenacetin, lidocaine, diltiazem and also hydroxyzine with a worth of +18 mV, −12 mV, −32 mV, +13 mV, −17 mV, −7 mV and also −32 mV respectively. Together is clean from Fig. 2, the differences in between the oxidation potential that cocaine and also the oxidization potential of the cut agents are much bigger compared to the little shifts observed once analysing mixtures. Benzocaine does, however, display more complex behaviour in mixture with cocaine. Back the mixture shows both the characteristic peaks the cocaine and also benzocaine, the voltammogram reveals an additional set of peaks in the 0.25–0.45 V range. These procedures are no observed once the individual components are measured individually and, therefore, it results from a specific interaction in between cocaine and also benzocaine, i m sorry is unknown at this point. However, the set of peaks is well isolated from the cocaine signal chin and, therefore, provides additional information about the presence of cocaine and benzocaine in a mixture. Minor second peaks are likewise visible at lower potentials because that lidocaine, diltiazem and also hydroxyzine, as soon as in mixture through cocaine, and also are thus advantageous for the evaluate of the redox processes in the mixtures.

Fig. 3 shows a partial overlap that the cocaine oxidation signal with the lidocaine oxidation signal. This slim overlap go not an outcome in a difficulty for cocaine detection. The used concentration of lidocaine in this section, family member to cocaine, is much greater than the median content of lidocaine uncovered in seized cocaine street samples. In 2014 and also 2015, 13.5% of the seized cocaine samples, analysed by NICC making use of accredited GC-MS and GC-FID techniques, consisted of lidocaine with an typical concentration the 5 wt%.

It is also clear native Fig. 3 that the signal intensity because that cocaine drops significantly when in mixture with levamisole. This observation likewise applies to the levamisole signal. In ~ this point, it is unsure what reasons this diminish in intensity for these components. Most importantly, cocaine could still be easily detected. Since we build a screening technique without quantification, the lessened intensity forms no difficulty for the application. The levamisole content supplied in the experiment was when again higher than the average content the levamisole in seized cocaine street samples. In 2014 and also 2015, 57% the the seized cocaine samples, analysed by NICC using accredited GC-MS and GC-FID techniques, included levamisole through an typical concentration of 12 wt%.

Voltammetry the street samples in solution

In stimulate to check the potential that the fingerprint method for the detection the cocaine in street samples, square-wave voltammograms of numerous seized street samples were videotaped in buffer solution (0.1 M KCl + 0.020 M KH2PO4 in ~ pH 7) and also corrected because that the background existing as excellent before. All solutions were made such that they all included 1 mM of cocaine and the equivalent voltammograms are displayed in Fig. 4. Prior to the analysis, the qualitative and quantitative composition of the street samples was identified at the nationwide Institute that Criminalistics and also Criminology (NICC) using accredited GC-MS and GC-FID methods.
Fig. 4 Baseline-corrected square-wave voltammetric responses (vs. Ag/AgCl) that street samples at ceiling carbon screen-printed electrodes in 0.1 M KCl + 0.020 M KH2PO4 buffer systems (pH 7). The dotted line represents the properties oxidation potential of cocaine at 1.04 V. The y-axis has actually the exact same scale in every voltammogram. Each solution was all set in such method that it has 1 mM that cocaine.

Fig. 4 mirrors that the cocaine height is plainly detectable in street samples containing phenacetin, caffeine, levamisole, boric acid, hydroxyzine and lidocaine, also when the cocaine amount is only 30 wt% as is the situation in the 3rd sample. Understanding that NICC in Belgium discovered that 95% of every seized cocaine samples in 2014 contained an ext than 35 wt% that cocaine, this method is really promising to explore further for rapid on-site screening. Also more, based upon the observations made in Fig. 2 and also 3, the existence of the cutting agents can be evidenced.

Two the the characteristic phenacetin peaks space clear and also sharp in the first sample at their characteristic potentials the 0.77 and also 0.35 V, whereas the signal for levamisole is also clearly visible in ~ its characteristic potential the 1.27 V in the second sample. The second sample plainly shows the redox processes of cocaine and also levamisole at your fingerprint potentials, i.e. 1.04 and also 1.27 V, respectively. The percentage cocaine is ca. 30% in the third sample, however, plainly visible in the square-wave voltammogram. In the fourth sample we watch a height at about 0.80 V, which is characteristic because that hydroxyzine. Also a very tiny wave is clearly shows at 0.10 V i beg your pardon is characteristic because that either hydroxyzine or diltiazem. A little peak is additionally visible at roughly 1.30 V, which suggests the visibility of caffeine. We were not able to detect the signal because that lidocaine in this particular street sample, yet this have the right to be defined by the really low concentration the the link in the sample (Voltammetry of flour street samples For easy on-site use, that is proper to recognize the samples straight in its powder form, fairly than in solution, to stop sample preparation. In order to perform so, we usage the on-site scan method, as is described in information in the experimental section. A conducting gelatine hydrogel was supplied as an electrolyte because that the electrochemical measurements.

Square-wave voltammograms of several seized street samples were recorded and also presented in Fig. 5, and also a blank to retain the an answer of the gelatine gel itself and also a sample only containing pure cocaine. A conditioning action was performed in ~ 0 V fairly than the previous favored 1.5 V in solution, come optimize the sensitivity towards cocaine.

Fig. 5 Baseline-corrected square-wave voltammetric responses (vs. Ag/AgCl) of flour street samples at bare carbon screen-printed electrodes utilizing a gelatin gel B hydrogel comprise 0.1 M KCl + 0.020 M KH2PO4 buffer equipment (pH 7) together electrolyte. The dotted heat represents the oxidation potential the cocaine at 0.97 V. The y-axis has the very same scale in every voltammogram.

Clearly, the gel itself causes an intense electrochemical signal around 1.30 V and also a tiny peak at 0.57 V. Any information in ~ ca. 1.30 V will, therefore, not be applicable come a certain cutting agent. However, the is clear that this method works exceptionally well for quick on-site cocaine detection. The cocaine height is really intense when pure cocaine is measured, as is clean from the second voltammogram in Fig. 5. The cocaine top is also well detectable for the street sample containing 23% levamisole and for the sample with only 30% cocaine and also an unknown amount of boric acid. A little shift in the optimal potentials is visible because that powders entrapped in the gelatine matrix compared to the solutions. The cocaine optimal is currently situated at a potential the 0.97 V rather of 1.04 V.

This information-rich and single run square-wave voltammetry method, using electrodes immobilized on the fingertip the a glove, holds significant promise for the fast on-site screening of suspiciously cargo and also persons on the presence of cocaine and its cut agents.


The reproducibility of the acquired signals in solution and powders was studied by performing five measurements, through each time a various SPE, on several of the earlier studied samples, all containing 1 mM cocaine. In systems we derived results concerning the height potential the cocaine because that pure cocaine and three street samples. A pure cocaine solution confirmed the characteristic top at 1.04 ± 0.02 V, while for a an initial street sample include 73% cocaine and 17% phenacetin, a second street sample include 76% cocaine, 3% caffeine, 10% hydroxyzine and also less than 1% lidocaine and a 3rd street sample include 30% cocaine and also an unknown lot of boric mountain showed top potentials the 1.06 ± 0.01 V, 1.03 ± 0.01 V and also 1.03 ± 0.01 V respectively.

The results display a maximal optimal potential typical deviation the ±20 mV, likely brought about by little differences in the internal reference electrodes between different SPE"s. The potential move are, however, tiny and don"t cause any problems to determine cocaine, likewise because these little shifts happen for the cutting agents together well.

In flour form, the very same experiment was performed for pure cocaine, using the conductive gelatin as electrolyte and the acquired peak potential worth was 0.97 ± 0.01 V, showing the robustness and also reproducibility that the approach. This security was assured by the rubber ring, immobilized ~ above the thumb of the fingertip machine as is described in the speculative section. This ring keeps the conductive gelatin in place and it guarantees a constant applied pressure on the electrode surface while both fingers room joined throughout the experiments, resulting in stable baselines. The small potential variation additionally shows the swiping the electrode surface over the flour doesn"t bring about a various electrochemical solution caused by damaged electrode surfaces. This is just one of the factors why graphite electrodes were used.

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Reagents and also materials

The cocaine·HCl traditional was purchased native Lipomed (Arlesheim, Switzerland). Requirements of phenacetin, diltiazem, lidocaine, procaine, hydroxyzine, benzocaine, paracetamol and myo-inositol to be purchased indigenous Sigma-Aldrich (Diegem, Belgium). Criter of benzoic acid and levamisole to be purchased indigenous Acros Organics (Geel, Belgium). Standards of caffeine, boric acid, glucose, maltose and starch were purchased indigenous VWR chemistry (Leuven, Belgium) and a typical of D-sorbitol was purchased indigenous Merck chemistry KGaA (Overijse, Belgium). Really cocaine street samples were obtained from the nationwide Institute because that Criminalistics and also Criminology (Brussels, Belgium). Gelatine gelatin B was supplied by PB gelatins (United Kingdom). Carbon ItalSens IS-C display screen Printed Electrodes (SPE) were purchased from PalmSens (Utrecht, The Netherlands) and also were used during all electrochemical measurements. The electrode surface ar area is 7.07 mm2. All laboratorium-based electrochemical dimensions were performed making use of a Metrohm μAutolab III Potentiostat and NOVA 1.11 software.

Synthesis that the conducting gel

A mixture that 2.5 wt% gelatine gelatin B in a 100 mM KCl and also 20 mM KH2PO4 buffer was heated in one Eppendorf tube to 50 °C for 15 minutes adhered to by added mixing until the solution ended up being homogeneous. The systems was then transferred to a syringe in which the hydrogel to be formed and also aged throughout the following 16 hours at room temperature before use in the experiments.

Determination the samples in solution

The buffer solution provided for the experiments to be optimized to acquire maximal top separation and also sensitivity. The 0.1 M KCl + 0.020 M KH2PO4 buffer enabled the to know of cocaine there is no overlapping the signal of the cutting agents, together is displayed in Fig. 2. Solutions of 1 mM cocaine and all cut agents were prepared in 0.1 M KCl + 0.02 M KH2PO4 buffer (pH 7) and stored in ~ 4 °C prior to analysis. Each systems was analyzed individually by putting a 50 μL drop on the SPE and also square-wave voltammetry was performed in order come detect characteristics redox processes for every substance. This was also performed for binary mixture of cocaine and a cut agent as well as for yes, really street samples.

On-site swiping method

suspiciously powders were analysed directly by utilizing a gelatine gel as a heavy electrolyte. The SPE was placed in a little SPE connector (with wires linked to the potentiostat) i beg your pardon was resolved on a metal ring. This ring is worn by the executer of the experiment ~ above the table of contents finger that a nitrile glove. The SPE was swiped gently over the suspicious powder in a manner which allowed some of the powder to be transferred onto the working electrode that the SPE. 100 μL that the conductive gelatin was added with a syringe to a small reservoir ~ above the thumb, surrounded by a little rubber ring. The rubber ring keeps the gelatin in place and was immobilized top top the thumb utilizing cyanoacrylate glue.

Both fingers were joined together, bring about completion of the electrochemical cell whereby upon the electrochemical measurement could be started. Each electrode and section of gelatin was provided only once.

Square-wave voltammetry

Square-wave voltammetry (SWV) to be performed come characterize the electrochemical fingerprint that cocaine (street) samples. A conditioning potential that 1.5 V was applied for 5 s, followed by a 2nd conditioning action of 5 s at 0 V prior to a scan from −0.1 V come a last potential of 1.5 V vs. Ag/AgCl to be performed. All scans were performed at a frequency of 10 Hz, with an amplitude of 25 mV, and a step potential that 5 mV. For the experiments through powders rather of solution, a single conditioning step of 5 s at 0 V to be performed.

Moving typical iterative elevator correction

A baseline correction an approach was built in the SWV procedure in the NOVA 1.11 software to instantly correct because that the elevating background present in bespeak to make the voltammograms less complicated to interpret. In brief, the method compares the worth of a data allude Ai come the values of the previous and also next data points Ai−1 and Ai+1. If the value of data allude Ai is higher than the median of the values of point out Ai−1 and also Ai+1 (as is the situation for an oxidation peak), the typical of the worths of Ai−1 and also Ai+1 will change the worth of Ai to build the corrected baseline. In all other situations when Ai is lower or the same as the median of Ai−1 and Ai+1, Ai will be the value provided for the repair baseline. This procedure was performed because that each two data clues in the voltammogram and repeated till the worth of Ai never exceeds the median of the worths of Ai−1 and also Ai+1 anymore, through a preferably of 1000 iterations. The repair baseline is now assembled and the background existing will it is in zero. Optimistic currents are only visible in ~ peaks of oxidation processes.


We have actually demonstrated the applicability of an electrochemical fingerprint strategy to determine cocaine and also its cutting agents in street samples. Direct evaluation with minimal sample ready is possible thanks to the integration of the screen-printed electrode in a glove and by making use of a conductive, versatile gelatine hydrogel as electrolyte. This new approach enables rapid on-site detection in ~ points of interest such as airports and harbours, by simply swiping the electrode system over the suspicious powder, join both fingers and also start the square-wave voltammetric measurement. Decision of the distinct electrochemical fingerprint that both cocaine and the cut agents in solution offers all crucial analytical information to finding cocaine and also the cut agents on-site in unknown suspiciously samples. The brand-new concept therefore holds substantial promise as a portable, on-site applicable screening method aimed in ~ the fast identification of cocaine/drugs (street) samples. To achieve this, a switch from a big potentiostat (like μAutolab III) to a miniaturized, portable potentiostat maker should be made. Through the rapid development of wireless systems and communication, the infection of results to a smartphone or a tablet would be of an extensive utility to on-site medicine investigations.


The authors identify BELSPO for capital the APTADRU project (BR/314/PI/APTADRU).

Notes and also references