Forensic Science International 192 (2009) 94–97

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Forensic Science International

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Voltammetric determination of cocaine in confiscated samples using a cobalt

hexacyanoferrate film-modified electrode
Érica Naomi Oiye a, Natalia Biziak de Figueiredo a, José Fernando de Andrade a,
Heloisa Maria Tristão b, Marcelo Firmino de Oliveira a,*
a
USP – Faculdade de Filosofia Ciências e Letras de Ribeirão Preto – Departamento de Quı´mica – 14040-901 – Ribeirão Preto, São Paulo, Brazil
b
SPTC – Nucleo de Perı´cias Criminalı´sticas de Ribeirão Preto – 14015-040 – Ribeirão Preto, São Paulo, Brazil

A R T I C L E I N F O A B S T R A C T

Article history: In this work, a fast, non destructive voltammetric method for cocaine detection in acetonitrile medium
Received 28 May 2009 using a platinum disk electrode chemically modified with cobalt-hexacyanoferrate (CoHCFe) film is
Received in revised form 4 August 2009 described. The deposition of CoHCFe film at platinum disk (working electrode) was carried out in
Accepted 5 August 2009
aqueous solution containing NaClO4 at 0.1 mol L1 as supporting electrolite. Stability studies of the film
Available online 31 August 2009
and subsequent voltammetric analysis of cocaine were made in acetonitrile medium with NaClO4 at
0.1 mol L1 as supporting electrolite. A reversible interaction between cocaine and CoHCFe at the film
Keywords:
produces a proportional decrease of original peak current, due to the formation of a complex between
Cocaine
Cobalt hexacyanoferrate
cocaine and cobalt ı́ons, with subsequent partial passivation of the film surface, being the intensity of
Forensic chemistry current decrease used as analytical signal for cocaine. A linear dependence of cocaine detection was
Chemically modified electrodes carried out in the range from 2.4  104 to 1.5  103 mol L1, with a linear correlation coefficient of
0.994 and a detection limit of 1.4  104 mol L1. The analysis of confiscated samples by the proposed
method indicated cocaine levels from 37% to 95% (m/m) and these results were validated by comparison
to HPLC technique, being obtained good correlation between both methods.
ß 2009 Elsevier Ireland Ltd. All rights reserved.

1. Introduction Actually, the analysis of apprehended samples of cocaine by

police laboratories is carried out by different methodologies, such
Cocaine [methyl(1R, 2R, 3S, 5S)-3-(benzoyloxy)-8-methyl-8- as colorimetric spot tests [3], spectrometric (FTIR, Raman, MS) [4]
azabicyclo [3,2,1] octane-2-carboxylate) (Fig. 1) – the main and chromatographic techniques (TLC, HPLC and GC [02]). In this
alkaloid produced by Erythroxylum coca plant – consists on a case, an interesting presumptive colorimetric chemical test for
central nervous system stimulant substance and causes pharma- cocaine (Scott test) [5] can be cited: an aqueous solution of cobalt
codependence [1]. Its human consumption can be made by thiocyanate is added to suspect samples of cocaine and, after
different ways, such as nasal aspiration of the powder and venous simple pretreatment, if an insoluble blue color mass is observed,
injection of the aqueous solution (for cocaine chloridrate) or by than cocaine can be present. Each cobalt ion can complex two
inhalation of its vapour form, when it is smoked (for free base molecules of cocaine, even though acidic or alcaline pH conditions
cocaine). The purified form of cocaine consists on a white, are used.
crystalline solid, with aromatic odor and soluble in several organic It is important to mention that, in forensic analysis, the
solvents. In alcaline pH solutions, cocaine is promptly converted to experimental results must prove the nature of the substance, once
benzoylecgonine, which is soluble in aqueous solutions [2]. these results can absolve or condemn people involved in criminal
After the observation of its collateral damages as a pharma- processes. In this context, an apprehended substance is commonly
cological compound along the history, cocaine actually consists on analyzed by different techniques, according to legislation of each
an illegal substance in most part of the world, making part of the country. As an example, the United States Department of Justice [6]
main constituent of police apprehensions, followed by hemp and classifies the chemical analysis techniques in three classes: A, B
synthetic drugs, resulting in an increased amount of scientific and C, according to specificity and less susceptibility to false-
efforts to analyze this compound quickly and in a simple way [1]. positive or negative errors, in this order. Table 1 indicates some
examples of these techniques. According to these norms, a
conclusive verdict is obtained only if two chemical analyses
* Corresponding author. Tel.: +55 16 3602 3750. (one by class A test and other by A, B or C test) or three exams (two
E-mail address: [email protected] (M.F.d. Oliveira). by class B tests and the third by B or C test) are provided. In fact,

0379-0738/$ – see front matter ß 2009 Elsevier Ireland Ltd. All rights reserved.
doi:10.1016/j.forsciint.2009.08.004
 É.N. Oiye et al. / Forensic Science International 192 (2009) 94–97 95

acetonitrile /water (95:5 v/v). A Rheodyne Model 7725 injection valve with a 20 mL
sample loop was used. A reversed-phase column Shimadzu Shim-pack C18
(250  6.0 mm I.D., 5 mm) was applied for all measurements with a guard column
(Shimadzu Shim-pack C18). Prior to use, mobile phase solvents were filtered
through a 0.45 mm filter (Millipore Milex) and degassed by ultrasonic couple into
HPLC system. An isocratic program was used for HPLC analysis were as follows:
wavelength detector set at 224 nm and flow-rate 1.0 mL min1.
All chemical reagents were of analytical grade and all aqueous solutions were
prepared using deionised water. Acetonitrile, cobalt chloride and potassium
hexacyanoferrate from Merck and sodium perchlorate and sodium bicarbonate
from Riedel de Haen were used in this work. Cocaine standard and cocaine samples
were obtained from a partnership between this research group and the criminal
Fig. 1. Molecular structure of cocaine. experts of laboratory of toxicological analysis – Institute of Criminalistics – in
Ribeirão Preto city – São Paulo, Brazil.

2.2. Solutions
Table 1
Some analytical techniques for drug determination used by USA Justice A 0.1 mol L1 NaClO4 in aqueous solution was prepared in order to work as
Department. supporting-electrolyte for preparation of the CoHCFe film. This aqueous solution of
supporting-electrolite was employed at the preparation of the solutions of CoCl2 in
Class A Class B Class C
1.0  102 mol L1 and K3[Fe(CN)6] also in 1.0  102 mol L1. A 0.1 mol L1
Infrared spectrometry Capilairy eletroforesis Colorimetric tests NaClO4 in acetonitrile solution was prepared in order to work as supporting-
Mass spectrometry Gas chromatography Fluorescence electrolyte for stability tests and electrochemical behavior of cocaine. This solution
spectroscopy was used for preparation of cocaine standard solution in 1.0  102 mol L1.
Nuclear magnetic Thin layer UV–vis Cocaine solutions of confiscated samples were prepared with previous pretreat-
resonance spectroscopy chromatography spectrophotometry ment of small aliquots of the water-soluble cocaine chloridrate samples with
Raman spectroscopy Liquid chromatography Melting point sodium bicarbonate aqueous solution, in order to remove HCl from its chloridrate
form. So, the cocaine free of chloridrate, which is insoluble in water, was removed
by filtration, rinsed with deionized water, dried and dissolved in acetonitrile
supporting-electrolite solution.
instrumental chromatographic and spectrometric techniques
In order to remove electroactive oxygen, all solutions were carried out with a
figure as the most employed at forensic analysis of drugs. previous flow of nitrogen gas during 15 min.
However, these systems are not available in all police laboratories,
due to the relatively high cost presented. 2.3. Preparation and application of the chemically modified electrode
Despite its applicability to the analysis of a wide range of
A platinum disk (work electrode) was polished until a mirror-like appearance
substances of human interest [7,8], electrochemical methods of
with alumina powder, then rinsed with water, cleaned in an ultrasonic aqueous
analysis do not figure as the most popular techniques employed at bath and again rinsed with water before use. Equal volumes of 0.5 mL of CoCl2
forensic laboratories. The electrochemical analysis of cocaine and 1.0  102 mol L1 and K3[Fe(CN)6] 1.0  102 mol L1 solutions were added to the
its metabolites for example, is extensively reported in the electrochemical cell containing 4.0 mL of aqueous solution of NaClO4 0.1 mol L1.
literature, including information about mechanisms of reaction The formation of CoHCFe film was obtained by 30 successive potential cycles from
0.1 to 0.7 V (vs. Ag/AgCl) using a scan rate of 100 mV s1. The stability of the
for this substance [9–11] and analytical applications such as electrodeposited film was tested in acetonitrile solution of NaClO4 0.1 mol L1,
dosage of confiscated samples [12–15], demonstrating the being applied 100 successive potential cycles at the film, with subsequent
applicability of these techniques. registration of the voltammograms. The obtainment of cocaine in different
As an improvement on electrochemical analysis, the chemical concentrations at the electrochemical cell, such as the analysis of the confiscated
samples, were provided by standard addition method.
modification of electrode surfaces using chemical films of interest
consists on the basis for development of electrochemical sensors
[16]. In this context, films of transition metal hexacyanoferrates 3. Results and discussion
such as Prussian Blue and its analogues [17] deserves special
consideration. Such modified electrodes are useful for a variety of 3.1. Formation of the CoHCFe film
charge-transfer studies including efforts to enhance rates of
electron transfer of solution substrates and the ability of solution The CoHCFe film was successfully electrodeposited at working
substrates to enter (or exit) the film can be controlled by choice of electrode surface. Its formation can be evidenced at Fig. 2, due to
suitable derivatising layer. This can be evidenced in an extensive the increase of both cathodic and anodic peak currents. The results
literature for this family of chemical modifiers [7,18–23]. showed that the electron transfer between the substrate and the
Considering the importance of electroanalytical methods at the CoHCFe film is the fast transport process. The peak currents
field of drug analyses and the versatility of electrochemical sensors increase linearly with scan rate and the relation iap/icp is around to
based on transition metal hexacyanoferrates, such as the known the unity, being consistent with reversible redox system beha-
chemical affinity between cobalt ions and cocaine, this work aims viour. Once cobalt(II) ions cannot be reduced in this potential
to investigate the electrochemical behavior of cocaine in non range, the redox peaks correspond to the surface-confined
aqueous medium using a cobalt hexacyanoferate-chemically hexacyanoferrate(II/III) redox couple [11], whose redox process
modified platinum electrode and its possible applicability for corresponds to the following reaction:
cocaine determination in confiscated samples. NaCoII ½FeIII ðCNÞ6  þ Naþ þ e Ð Na2 CoII ½FeII ðCNÞ6  (1)

2. Experimental
The formal potential of +0.58 V vs. Ag/AgCl was obtained by
averaging the cathodic and anodic peak potentials.
2.1. Apparatus and chemicals

Measurements of cyclic voltammetry and linear sweep voltammetry were 3.2. Stability studies of the CoHCFe film
carried out using a mAutoLabIII potentiostat, under the control of a microcomputer.
A 5.0 mL conventional electrochemical cell was employed with a Metrohm
After its formation in aqueous medium, the chemically
platinum disk as working electrode, a Ag/AgCl (saturated aqueous KCl) reference
electrode and a platinum spiral auxiliary electrode.
modified electrode was dried at room temperature and applied
Chromatographic analysis of cocaine samples were carried out in a Shimadzu at the organic medium with acetonitrile containing NaClO4
HPLC apparatus, used in isocratic conditions with a mobile phase consisting of 0.1 mol L1 as supporting electrolite. The choice of this solvent
96 É.N. Oiye et al. / Forensic Science International 192 (2009) 94–97

behavior: a considerable increase in the relation iap/icp is observed;

the formal potential for hexacyanoferrate(II/III) redox couple was
obtained at 0.78 V (vs. Ag/AgCl), indicating a shift of 200 mV to
anodic region and a decrease of amperometric sensitivity is
observed in comparison to aqueous system. Additionally, a
difference between Eap and Ecp higher than 100 mV was observed
for this redox couple in acetonitrile, due to the more resistive
medium in relation to water. This behavior is also in accordance to
the electrochemical behavior of Prussian Blue analogues in
acetonitrile [23].

3.3. Electrochemical behavior of cocaine at CoHCFe film

The presence of cocaine species at the electrochemical system

produces a decrease of both peak currents of the CoHCFe film.
Considering the increase in the relation iap/icp for acetonitrile
medium, anodic peak currents were employed in the cocaine
dosage. A reversible interaction between cocaine and the
deposited film is observed, once a restoration of peak current
magnitudes is produced when the modified electrode is cleaned
and applied at a free cocaine-supporting electrolyte solution. The
linearity of this current decrease can be observed at Fig. 4. A linear
correlation coefficient of 0.994 and a standard deviation (SD) value
Fig. 2. CoHCFe film formation. Supporting-electrolyte: 0.1 mol L1 NaClO4 solution; of 1.8  107 A were observed for this dependence, and its
area of the platinum disk electrode: 7 mm2; number of cycles: 30; scan rate: correspondent equation was:
100 mV s1.
1
iap ¼ 2:7 mA  3:8  103 mA mol L ½cocaine (2)
is based on the fact that both forms of apprehended samples of
cocaine (free basis and cocaine chloridrate) present good solubility These results allowed a detection limit (LOD) of 1.4  104 mol L1
in this medium. In aqueous medium it is not possible to and a quantification limit (LOQ) of 4.7  104 mol L1 using the
dissolve crack samples, for example, which contains the free basis relations of 3SD/m and 10SD/m, respectively, where m is the
species of cocaine. Successive potential scanning in acetonitrile amperometric sensitivity of the curve [7].
showed that, after 100 cycles, there was a decrease of only 6% in the Based on the partial passivation of film surface by cocaine-
peak current, indicating good stability of the CoHCFe film, as cobalt complex, which blocks Na+ mobility for the subsequent
presented at Fig. 3. electron transfer of the FeII/FeIII system, the detection of cocaine is
The exchange from aqueous medium to a more resistive organic provided without redox stages or degradation of the molecule,
medium exhibited peculiar differences in terms of electrochemical consisting on a non destructive method for cocaine dosage.

Fig. 3. Study of stability of CoHCFe film in acetonitrile medium after 100

cycles of potential. Supporting-electrolyte: 0.1 mol L1 NaClO4; scan rate: Fig. 4. Influence of cocaine concentration at the voltammetric answer of the CoHCFe
100 mV s1. film: successive 100 mL additions of cocaine standard solution. v = 100 mV/s.
 É.N. Oiye et al. / Forensic Science International 192 (2009) 94–97 97

Table 2 Acknowledgements
A comparison between the results obtained in triplicate by voltammetric and
chromatographic methods for cocaine determination in confiscated samples (LSV,
linear sweep voltammetry; HPLC, high performance liquid chromatography; SD, The authors acknowledge to Fundação de Amparo à Pesquisa do
standard deviation; CV, coefficient of variation). Estado de São Paulo (FAPESP) and Conselho Nacional de Desenvol-
vimento Cientı́fico e Tecnológico (CNPq) for the financial support.
Sample LSV HPLC

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