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Oliveira, L. H. Marcolino Júnior and M. Bergamini, Anal. Methods, 2019, DOI: 10.1039/C9AY00555B.
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11 Carbon Black Composite Electrode for Flow Injection
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EVA/CB composite electrode as the working electrode. For (methodology recommended by the Brazilian
3 comparative studies others solid carbon-based electrodes Pharmacopedia)21.
4 were used as working electrode: Glassy carbon electrode (GCE)
5 with diameter of 3 mm by Metrohm, Screen printed carbon
6 electrode (SPCE), provided by Prof. Craig E. Banks from 3. Results and Discussion
7 Manchester Metropolitan University19, Epoxy resin and 3.1. Electrochemical behavior of hydrochlorothiazide (HCTZ)
8 graphite composite electrode (GEE)20. The SPCE (3 mm The first step addressed for the development of the FIA
9 diameter working electrode) were fabricated with a stencil procedure for the determination of HCTZ in pharmaceutical
10 designs using a microDEK 1760RS screen-printing machine formulations and synthetic urine samples was the investigation
11 (DEK,Weymouth, UK). A metallic thread is placed on the of the electrochemical behavior of the drug (Fig. 2A). Cyclic
12 female connector. Then, a sheet of circular copper is welded. voltammograms were obtained in the absence and in the
13 Subsequently, the PVC tube (6 mm diameter) is placed around presence of a sufficient amount of HCTZ to obtain a significant
14 the connector. The prepared composite (epoxy resin + process for the visualization and evaluation of the
15 graphite) is introduced into the virtual cavity this tube. performance of the proposed electrode (1.0 mmol L-1 of HCTZ
For pH measurements, a Metrohm pH-meter with a combined
16 in 0.04 mol L-1 BR buffer solution at 50 mV s-1). One of the
pH reference electrode was used.
17 advantages of the composite electrode proposed is its high
FIA experiments were carried out using a flow cell with an
18 effective volume of 95 L. The working electrode (EVA/CB
mechanical resistance promoted by the presence of EVA. Thus,
19 electrode), reference electrode (Ag/AgCl/KCl, 3.0 mol L-1) and
other carbon-based electrodes with similar feature were used
20 in order to compare the voltammetric profile of HCTZ (Fig. 2B).
the platinum auxiliary electrode were introduced through
21 holes in its cover. The electrochemical flow cell was inserted in 30 In absence of HCTZ
22 a one-channel flow injection analysis system7. The system was
In the presence de HCTZ
I/ A
Switzerland) and a manual homemade injector of
25 polyurethane. The manifold connections were made with 10
26 tygon tubing (0.5 mm i.d.). Britton-Robinson (BR) buffer
27 solution (0.04 mol LR pH 7.5) was used as the carrier solution. 0
A
28 The analytical path was 30 cm long and the entire flow -0.3 0.0 0.3 0.6 0.9 1.2
29 injection system was kept at room temperature. E / V (vs. Ag/AgCl/KCl, 3.0 mol L )
-1
30 GCE
2.4. Flow injection analysis
31 300 SPCE
EVA/CB
32
-2
Flow injection experiments were carried out using the EVA/CB GEE
j / A cm
200
33 composite electrode as an amperometric detector. All
34 experimental parameters (flow rate, volume of injection and 100
35 potential applied) were studied by analyzing the sensor
response to HCTZ oxidation process in 0.04 mol LR BR buffer 0
36 B
solution, pH 7.5. Parameters such as detection potential, flow
37 -0.3 0.0 0.3 0.6 0.9 1.2
rate and volume of injection were evaluated and chosen based
38 E / V (vs. Ag/AgCl/KCl, 3.0 mol L )
-1
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probably caused by a minimal dispersion of the analytical
3 solution 27. Thus, a volume of injection of 100 µL was selected A e B
3.0 3.0
4 for furthers studies.
5 Flow rate of the carrier solution is a hydrodynamic parameter
I/ A
6
I/ A
that plays a key role since it changes the efficiency of mass 2.0 d d 2.0
7 transport of the analyte from bulk solution to EVA/CB
8 electrode surface. The influence on the peak current was
9 evaluated for flow rate values in the range of 1.7 to 8.0 mL c c 1.0
1.0
10 min-1 using potential of detection of 900 mV and sample
11 volume of 100 µL (Fig.4 C). Sensitivity increased continuously b b
S3
8 d We gratefully acknowledge financial support from Brazilian
9 1.0
c agencies Fundação Araucária, CAPES and CNPQ.
c
10 S2
11 0.5 b b a
12 S1 References
13
0.0 1. Y. V. Pleskov, M. D. Krotova, V. V. Elkin and E. A.
14 0 300 600 900 1200
15 t/s Ekimov, Electrochimica Acta, 2016, 201, 268-273.
16 Fig.6:Transient current signals obtained (n=3) for HCTZ solutions: (a) 2. P. R. d. Oliveira, M. M. Oliveira, A. J. G. Zarbin, L. H.
Marcolino-Junior and M. F. Bergamini, Sensors and
17 1.0 x 10-5, (b) 2.0 x 10-5, (c) 5.0 x 10-5, (d) 1.0 x 10-4 and (e) 2.0 x 10-4;
Actuators B: Chemical, 2012, 171–172, 795-802.
18 and spiked urine samples solutions in three levels of concentration:
U1- 1.0 x 10-5 mol L-1, U2 - 5.0 x 10-5 mol L-1 and U3 - 1.0 x 10-4 mol L- 3. F. R. Caetano, A. Gevaerd, E. G. Castro, M. F.
19 Bergamini, A. J. G. Zarbin and L. H. Marcolino-Junior,
1. Conditions: 0.04 mol L-1 BR buffer solution (pH 7.5), applied
20 Electrochimica Acta, 2012, 66, 265-270.
potential of 900 mV, sample volume of 100 µL and flow rate of 5.3
21 4. D. Talarico, S. Cinti, F. Arduini, A. Amine, D. Moscone
mL min-1.
22 and G. Palleschi, Environmental Science & Technology,
23 2015, 49, 7934-7939.
The commercial sample was analyzed under the same
24 conditions (not shown). The amounts of HCTZ found in the 5. F. Arduini, F. D. Giorgio, A. Amine, F. Cataldo, D.
25 samples using the proposed method (53.8 mg/tablet) were in Moscone and G. Palleschi, Analytical Letters, 2010, 43,
26 agreement with those obtained by the B;R' spectroscopy 1688-1702.
27 methodology (52.4 ± 4.10 mg/tablet) at a 95% confidence level 6. A. M. Henderson, IEEE Electrical Insulation Magazine,
28 (n = 3), the labeled value being 50.0 mg/tablet. Statistical 1993, 9, 30-38.
29 analyses for the assay results showed good concordance 7. F. Calegari, L. P. de Souza, M. M. Barsan, C. M. A.
30 between values obtained by the proposed method and the Brett, L. H. Marcolino-Junior and M. F. Bergamini,
31 comparative one (applying the paired sample t-test at 95% Sensors and Actuators B: Chemical, 2017, 253, 10-18.
8. B. Beermann, M. Groschinsky-Grind and A. Rosén,
32 confidence level).
Clinical Pharmacology and Therapeutics, 1976, 19, 531-
33
537.
34 Conclusions 9. J. D. Duarte and R. M. Cooper-Dehoff, Expert Review
35 of Cardiovascular Therapy, 2010, 8, 793-802.
36 Excellent analytical performance of EVA/CB composite 10.L. L. VERONEZ and M. J. S. SIMÕES, Análise da
37 electrode as amperometric cell was verified for HCTZ prescrição de medicamentos de pacientes hipertensos
38 determination. The proposed electrode has shown a good atendidos pelo SUS da rede municipal de saúde de
39 electrochemical behaviour allowing HCTZ determination at Rincão - SP, 2009.
40 potential values similar to others solid carbon-based 11.J. P. Andrade and F. Nobre, Arquivos Brasileiros de
41 electrodes. In addition, the sensor is a low-cost material when Cardiologia, 2010, 95, I-III.
42 compared to others carbonaceous material as carbon 12.H.-J. Guchelaar, L. Chandi, O. Schouten and W. Van
43 nanotubes or glassy carbon. It is an easy-preparation den Brand, Fresenius' journal of analytical chemistry,
44 composite that is mechanically and chemically more resistant 1999, 363, 700-705.
45 than other similar electrodes based on carbon paste. 13.WADA, 2017 List of Prohibited Substances and
46 A new electroanalytical methodology proposed for the Methods, https://www.wada-
determination of HCTZ presents several advantages when ama.org/en/media/news/2016-09/wada-publishes-
47
compared to B;R' spectroscopy, especially regarding to 2017-prohibited-list, (accessed 21/04/2017, 2017).
48
simplicity (the proposed method not require sample 14.R. Nicoli, D. Guillarme, N. Leuenberger, N. Baume, N.
49 preparation), cost and speed of analysis (128 injections hR ). Robinson, M. Saugy and J.-L. Veuthey, Analytical
50 Besides that, the proposed methodology presents adequate Chemistry, 2016, 88, 508-523.
51 sensitivity and useful linear dynamic range for determination 15.F. Badoud, D. Guillarme, J. Boccard, E. Grata, M.
52 of HCTZ in human urine samples and pharmaceutical Saugy, S. Rudaz and J.-L. Veuthey, Forensic Science
53 formulations analysis and allows its application as point-of- International, 2011, 213, 49-61.
54 care device in the quantification of HCTZ in analysis of 16.W. B. S. Machini and M. F. S. Teixeira, Biosensors and
55 laboratory routines and control of doping. Bioelectronics, 2016, 79, 442-448.
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17.D. T. Gimenes, M. C. Marra, J. M. de Freitas, R. A.
3 Abarza Muñoz and E. M. Richter, Sensors and Actuators
4 B: Chemical, 2015, 212, 411-418.
5 18.P. F. Pereira, M. C. Marra, R. A. A. Munoz and E. M.
6 Richter, Talanta, 2012, 90, 99-102.
7 19.L. M. Ochiai, D. Agustini, L. C. Figueiredo-Filho, C. E.
8 Banks, L. H. Marcolino-Junior and M. F. Bergamini,
9 Sensors and Actuators B: Chemical, 2017, 241, 978-984.
10 20.M. I. Pividori and S. Alegret, Analytical letters, 2003,
11 36, 1669-1695.
12 21.Journal, 2010.
13 22.H. Beitollahi, M. Hamzavi and M. Torkzadeh-Mahani,
14 Materials Science and Engineering: C, 2015, 52, 297-305.
15 23.H. Karimi-Maleh, M. R. Ganjali, P. Norouzi and A.
Bananezhad, Materials Science and Engineering: C,
16
2017, 73, 472-477.
17
24.S. Tajik, M. A. Taher and H. Beitollahi, Journal of
18 Electroanalytical Chemistry, 2013, 704, 137-144.
19 25.B. Rezaei and S. Damiri, IEEE Sensors Journal, 2008, 8,
20 1523-1529.
21 26.C. M. A. Brett and A. M. O. Brett, Electrochemistry:
22 Principles, Methods, and Applications, Oxford University
23 Press, 1993.
24 27.V. V. Kuznetsov, Talanta, 2018, 187, 237-245.
25 28.D. T. Gimenes, M. C. Marra, R. A. A. Muñoz, L. Angnes
26 and E. M. Richter, Anal. Methods, 2014, 6, 3261-3267.
27 29.B. C. Lourencao, R. A. Medeiros and O. Fatibello-
28 Filho, J. Electroanal. Chem., 2015, 754, 154-159.
29 30.J. Ouyang, W. R. G. Baeyens, J. Delanghe, G. Van der
30 weken and A. C. Calokerinos, Talanta, 1998, 46, 961-
31 968.
31.D. T. Gimenes, M. C. Marra, J. M. de Freitas, R. A. A.
32
Muñoz and E. M. Richter, Sensors and Actuators B:
33
Chemical, 2015, 212, 411-418.
34 32.O. Abdel Razak, Journal of Pharmaceutical and
35 Biomedical Analysis, 2004, 34, 433-440.
36
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