Application and prospect of carbon nanomaterials in electroanalysis for detection of illicit drugs in sports

Yan, Jiahui

doi:10.1590/1517-7076-RMAT-2024-0177

Jiahui Yan

Henan University of Science and Technology, Sports Institute. 471000, Luoyang, China.

https://orcid.org/0009-0002-0556-3614

Corresponding Author: Jiahui Yan, e-mail: yanjiahui1017@126.com

Figures (11)
Tables (2)

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Figure 1
Categories of drugs are abused by athletes.

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Figure 2
Schematic model of the control of red blood cell production and the sites of action of erythropoiesis-stimulating agents [⁴⁹[49] SALAMIN, O., KUURANNE, T., SAUGY, M., et al., “Erythropoietin as a performance-enhancing drug: Its mechanistic basis, detection, and potential adverse effects”, Molecular and Cellular Endocrinology, v. 464, pp. 75–87, Mar. 2018. doi: http://doi.org/10.1016/j.mce.2017.01.033. PubMed PMID: 28119134.
https://doi.org/10.1016/j.mce.2017.01.03... ].

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Figure 3
(A) Typical CVs observed for 1.0 μM nandrolone in PBS of pH 7.2 at a bare (- - -) and fullerene-C60-modified (—) GCE electrode [⁷⁷[77] GOYAL, R.N., GUPTA, V.K., BACHHETI, N., “Fullerene-C60-modified electrode as a sensitive voltammetric sensor for detection of nandrolone—An anabolic steroid used in doping”, Analytica Chimica Acta, v. 597, n. 1, pp. 82–89, Jul. 2007. doi: http://doi.org/10.1016/j.aca.2007.06.017. PubMed PMID: 17658316.
https://doi.org/10.1016/j.aca.2007.06.01... ]. (B) The EIS response of the MIP/GO electrode towards testosterone in different concentrations [⁸²[82] LIU, W., MA, Y., SUN, G., et al., “Molecularly imprinted polymers on graphene oxide surface for EIS sensing of testosterone”, Biosensors & Bioelectronics, v. 92, pp. 305–312, Jun. 2017. doi: http://doi.org/10.1016/j.bios.2016.11.007. PubMed PMID: 27836607.
https://doi.org/10.1016/j.bios.2016.11.0... ].

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Figure 4
Rapid on-site detection of illicit drugs with a portable electrochemical device [⁸³[83] PARRILLA, M., SLOSSE, A., VAN ECHELPOEL, R., et al., “Rapid on-site detection of illicit drugs in smuggled samples with a portable electrochemical device”, Chemosensors (Basel, Switzerland), v. 10, n. 3, pp. 108, Mar. 2022. doi: http://doi.org/10.3390/chemosensors10030108.
https://doi.org/10.3390/chemosensors1003... ].

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Figure 5
Timeline of carbon nanomaterials.

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Figure 6
Predominant interactions involved between immobilized molecules and GO/RGO [⁸⁸[88] CHAUDHARY, K., KUMAR, K., VENKATESU, P., et al., “Protein immobilization on graphene oxide or reduced graphene oxide surface and their applications: Influence over activity, structural and thermal stability of protein”, Advances in Colloid and Interface Science, v. 289, pp. 102367, Mar. 2021. doi: http://doi.org/10.1016/j.cis.2021.102367. PubMed PMID: 33545443.
https://doi.org/10.1016/j.cis.2021.10236... ].

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Figure 7
(A) The photos of 10 μL GO (a), MWNT (b), MWNT-doped-GO (c) casted on ITO glass; SEM images of GO (B), MWNT (C), MWNT-doped-GO (D) casted on Si plate.

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Figure 8
(A) D-mannitol sensor based on MIP on electrode modified with RGO decorated with AuNPs [¹⁰⁸[108] BELUOMINI, M.A., DA SILVA, J.L., SEDENHO, G.C., et al., “D-mannitol sensor based on molecularly imprinted polymer on electrode modified with reduced graphene oxide decorated with gold nanoparticles”, Talanta, v. 165, pp. 231–239, Apr. 2017. doi: http://doi.org/10.1016/j.talanta.2016.12.040. PubMed PMID: 28153247.
https://doi.org/10.1016/j.talanta.2016.1... ]. (B) An electrochemical sensor based on Co₂O₃/RGO nanocomposite for detection of clonazepam [¹⁰⁹[109] GARIMA, SACHDEV, A., MATAI, I., “An electrochemical sensor based on cobalt oxyhydroxide nanoflakes/reduced graphene oxide nanocomposite for detection of illicit drug-clonazepam”, Journal of Electroanalytical Chemistry (Lausanne, Switzerland), v. 919, pp. 116537, Aug. 2022. doi: http://doi.org/10.1016/j.jelechem.2022.116537.
https://doi.org/10.1016/j.jelechem.2022.... ].

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Figure 9
Schematic procedures and filtration device structures for preparing SWCNTs electrodes by flash foam stamp-assisted template filtration [¹²⁰[120] YANG, J., HE, D., ZHANG, N., et al., “Disposable carbon nanotube-based antifouling electrochemical sensors for detection of morphine in unprocessed coffee and milk”, Journal of Electroanalytical Chemistry (Lausanne, Switzerland), v. 905, pp. 115997, Jan. 2022. doi: http://doi.org/10.1016/j.jelechem.2021.115997.
https://doi.org/10.1016/j.jelechem.2021.... ].

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Figure 10
Simultaneous biosensing of nandrolone and testosterone using DTMIP/C60/MWCNT-Gr-IL/ITO [¹¹¹[111] JALALVAND, A.R., RASHIDI, Z., KHAJENOORI, M., “Sensitive and selective simultaneous biosensing of nandrolone and testosterone as two anabolic steroids by a novel biosensor assisted by second-order calibration”, Steroids, v. 189, pp. 109138, Jan. 2023. doi: http://doi.org/10.1016/j.steroids.2022.109138. PubMed PMID: 36379297.
https://doi.org/10.1016/j.steroids.2022.... ].

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Figure 11
Mindmap of challenges and future prospects of carbon nanomaterials in electroanalysis for detection of illicit drugs in sports.

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Table 1
Summarizes the recent developed graphene based electrochemical sensor for detection of illicit drugs in sports.

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Table 2
Summarizes the recent developed CNT based electrochemical sensor for detection of illicit drugs in sports.

SENSOR	ANALYTE	LINEAR DETECTION RANGE	LIMIT OF DETECTION	REAL SAMPLE PERFORMANCE	REF.
Au/GO/GCE	Nandrolone	1 to 100 μM	4 nM	The sensor was used to determine Nandrolone levels in serum and urine samples of athletes who were administered Nandrolone. The results showed good agreement with ELISA kit, with RSD values of 3.10–4.33%.	[¹¹⁰[110] LI, C., XIAO, Y., LIU, J., et al., “Determination of anabolic steroid as doping agent in serum and urine of athletes by using an electrochemical sensor based on the graphene-gold hybrid nanostructure”, International Journal of Electrochemical Science, v. 17, n. 7, pp. 220766, Jul. 2022. doi: http://doi.org/10.20964/2022.07.70. https://doi.org/10.20964/2022.07.70... ]
DTMIP/C60/MWCNT-Gr-IL/ITO	Nandrolone decanoate and testosterone decanoate	–	0.05 nM for nandrolone and 0.5 nM for testosterone	The biosensor was successfully applied to the analysis of ND and TS in urine samples from bodybuilder athletes and the results showed good agreement with HPLC reference method. Recoveries from spiked urine samples were in the range of 96.3–106% for both analytes.	[¹¹¹[111] JALALVAND, A.R., RASHIDI, Z., KHAJENOORI, M., “Sensitive and selective simultaneous biosensing of nandrolone and testosterone as two anabolic steroids by a novel biosensor assisted by second-order calibration”, Steroids, v. 189, pp. 109138, Jan. 2023. doi: http://doi.org/10.1016/j.steroids.2022.109138. PubMed PMID: 36379297. https://doi.org/10.1016/j.steroids.2022.... ]
MIP/Au/GCE	19-nortestosterone	5 to 95 μM	3 nM	The sensor was used to detect 19-NT in urine samples from athletes who were administered Nandrodek. The results showed good agreement between the amperometric sensor and ELISA kit assay, with relative standard deviations between 3.09–4.38% for the amperometric method.	[¹⁰⁷[107] ZHAO, X., ZHAN, B., NIE, W., “Electrochemical determination of nandrolone as a doping agent in sport by molecularly imprinted polymers and Au nanoparticles hybrid nanostructured electrode in biological fluids”, International Journal of Electrochemical Science, v. 17, n. 8, pp. 220856, Aug. 2022. doi: http://doi.org/10.20964/2022.08.52. https://doi.org/10.20964/2022.08.52... ]
MIP on GOsurface	Testosterone	1 fM to 1 μM	0.4 fM	The sensor was used to detect testosterone in diluted human serum samples. Spike recoveries ranged from 98.6% to 104.2%.	[⁸²[82] LIU, W., MA, Y., SUN, G., et al., “Molecularly imprinted polymers on graphene oxide surface for EIS sensing of testosterone”, Biosensors & Bioelectronics, v. 92, pp. 305–312, Jun. 2017. doi: http://doi.org/10.1016/j.bios.2016.11.007. PubMed PMID: 27836607. https://doi.org/10.1016/j.bios.2016.11.0... ]
RGO/GCE	Testosterone	2.0 to 210.0 nM	0.1 nM	The sensor was used for quantification of testosterone in biological fluids (urine and plasma) and drug (ANDRONE®100) with good recovery.	[¹¹²[112] HEIDARIMOGHADAM, R., AKHAVAN, O., GHADERI, E., et al., “Graphene oxide for rapid determination of testosterone in the presence of cetyltrimethylammonium bromide in urine and blood plasma of athletes”, Materials Science and Engineering C, v. 61, pp. 246–250, Apr. 2016. doi: http://doi.org/10.1016/j.msec.2015.12.005. PubMed PMID: 26838847. https://doi.org/10.1016/j.msec.2015.12.0... ]
PDA/Au@RGO	Testosterone	25 to 200 μM	4.2 μM	The sensor was used to detect testosterone spiked in pH 7.4 PBS buffer. The electrocatalytic conversion of testosterone to 6β-OH testosterone by the sensor was confirmed using HPLC-MS.	[¹¹³[113] XU, X., BAI, G., SONG, L., et al., “Fast steroid hormone metabolism assays with electrochemical liver microsomal bioreactor based on polydopamine encapsulated gold-graphene nanocomposite”, Electrochimica Acta, v. 258, pp. 1365–1374, Dec. 2017. doi: http://doi.org/10.1016/j.electacta.2017.11.195. https://doi.org/10.1016/j.electacta.2017... ]
Graphene-modified SPE	Methamphetamine	1–500 μM	0.3 μM	Street samples containing methamphetamine: Detected methamphetamine in 8 out of 9 samples (89% true positive rate)	[¹¹⁴[114] TRUTA, F., DRAGAN, A.-M., TERTIS, M., et al., “Electrochemical Rapid Detection of Methamphetamine from Confiscated Samples Using a Graphene-Based Printed Platform”, Sensors (Basel), v. 23, n. 13, pp. 6193, Jan. 2023. doi: http://doi.org/10.3390/s23136193. PubMed PMID: 37448052. https://doi.org/10.3390/s23136193... ]
Graphene/AuNP modified electrode	Cocaine	1 nM to 500 nM	1 nM	–	[¹¹⁵[115] JIANG, B., WANG, M., CHEN, Y., et al., “Highly sensitive electrochemical detection of cocaine on graphene/AuNP modified electrode via catalytic redox-recycling amplification”, Biosensors & Bioelectronics, v. 32, n. 1, pp. 305–308, Feb. 2012. doi: http://doi.org/10.1016/j.bios.2011.12.010. PubMed PMID: 22204778. https://doi.org/10.1016/j.bios.2011.12.0... ]
3D-MRGO/PA/AuNP/aptamer based impedimetric aptasensor	Cocaine	0.09 to 85 nM	0.029 nM	The aptasensor was applied to detect cocaine in spiked urine and serum samples with satisfactory recoveries. Relative standard deviations ranged from 2.4% to 3.9%.	[¹¹⁶[116] HASHEMI, P., BAGHERI, H., AFKHAMI, A., et al., “Fabrication of a novel aptasensor based on three-dimensional reduced graphene oxide/polyaniline/gold nanoparticle composite as a novel platform for high sensitive and specific cocaine detection”, Analytica Chimica Acta, v. 996, pp. 10–19, Dec. 2017. doi: http://doi.org/10.1016/j.aca.2017.10.035. PubMed PMID: 29137703. https://doi.org/10.1016/j.aca.2017.10.03... ]
CRGO-GCE	Furosemide	1–600 μM	0.7 μM	Recovery between 89–99% in spiked seawater samples.	[¹¹⁷[117] VASCONCELOS, S.C., RODRIGUES, E.M., DE ALMEIDA, L.G., et al., “An improved drop casting electrochemical strategy for furosemide quantification in natural waters exploiting chemically reduced graphene oxide on glassy carbon electrodes”, Analytical and Bioanalytical Chemistry, v. 412, n. 26, pp. 7123–7130, Oct. 2020. doi: http://doi.org/10.1007/s00216-020-02845-9. PubMed PMID: 32737552. https://doi.org/10.1007/s00216-020-02845... ]

SENSOR	ANALYTE	LINEAR DETECTION RANGE	LIMIT OF DETECTION	REAL SAMPLE PERFORMANCE	REF.
CeO₂/CNTs/GCE	Methyltestosterone	0–10 μg/mL	0.3 ng/mL	The sensor was tested in real human blood serum samples from athlete volunteers. Suitable recovery values (94.50–98.00%) and acceptable relative standard deviation (RSD) values (3.97–5.03%) were obtained.	[⁹⁴[94] PENG, C., LIU, H.C., WU, M., et al., “A sensitive electrochemical sensor for detection of methyltestosterone as a doping agent in sports by CeO2/CNTs nanocomposite”, International Journal of Electrochemical Science, v. 18, n. 2, pp. 25–30, Feb. 2023. doi: http://doi.org/10.1016/j.ijoes.2023.01.014. https://doi.org/10.1016/j.ijoes.2023.01.... ]
ZnO/CNT	Morphine	0.1 to 700 μM	0.06 μM	Successfully applied to detect morphine in pharmaceutical injection solution and urine samples	[¹¹⁹[119] AFSHARMANESH, E., KARIMI-MALEH, H., PAHLAVAN, A., et al., “Electrochemical behavior of morphine at ZnO/CNT nanocomposite room temperature ionic liquid modified carbon paste electrode and its determination in real samples”, Journal of Molecular Liquids, v. 181, pp. 8–13, May. 2013. doi: http://doi.org/10.1016/j.molliq.2013.02.002. https://doi.org/10.1016/j.molliq.2013.02... ]
MWNTs-doped GO/GCE	Morphine	0.07–17 μM	0.05 μM	Tested in human blood serum and urine samples, recoveries ranged from 91.2–100.3% in serum and 94.2–106.3% in urine.	[¹⁰⁰[100] LI, Y., ZOU, L., LI, Y., et al., “A new voltammetric sensor for morphine detection based on electrochemically reduced MWNTs-doped graphene oxide composite film”, Sensors and Actuators. B, Chemical, v. 201, pp. 511–519, Oct. 2014. doi: http://doi.org/10.1016/j.snb.2014.05.034. https://doi.org/10.1016/j.snb.2014.05.03... ]
NiO/CNTs ionic liquid CPE	Morphine	0.05–520 μM	0.01 μM	The sensor was successfully applied for the determination of morphine in injection solution and urine samples. The results showed good recovery and accuracy.	[¹²²[122] SANATI, A.L., KARIMI-MALEH, H., BADIEI, A., et al., “A voltammetric sensor based on NiO/CNTs ionic liquid carbon paste electrode for determination of morphine in the presence of diclofenac”, Materials Science and Engineering C, v. 35, pp. 379–385, Feb. 2014. doi: http://doi.org/10.1016/j.msec.2013.11.031. PubMed PMID: 24411391. https://doi.org/10.1016/j.msec.2013.11.0... ]
P-L-Arg/CNTs/CPE	Methadone	0 to 600 μM	22 nM	Tested in urine samples of athletes. Recovery range: 98.86% to 99.91%. RSD range: 3.56% to 4.41%	[¹²¹[121] SONG, Y., SUN, J., LI, Y., et al., “Electrochemical detection of Methadone by use of poly-l- arginine/carbon nanotubes composite modified carbon paste electrode (P-L-Arg/CNTs/CPE) in human urine”, International Journal of Electrochemical Science, v. 17, n. 12, pp. 221239, Dec. 2022. doi: http://doi.org/10.20964/2022.12.43. https://doi.org/10.20964/2022.12.43... ]
MWCNTs/SnO₂–Zn₂SnO₄/CPE	Morphine ; Codeine	Morphine: 0.1–310 μM Codeine: 1–600 μM	Morphine: 0.009 μM Codeine: 0.009 μM	Morphine: Recovery 96.4–103.5% in human urine samples. Codeine: Recovery 97.0–100.3% in human urine and cough syrup samples.	[¹²³[123] TAEI, M., HASANPOUR, F., HAJHASHEMI, V., et al., “Simultaneous detection of morphine and codeine in urine samples of heroin addicts using multi-walled carbon nanotubes modified SnO2–Zn2SnO4 nanocomposites paste electrode”, Applied Surface Science, v. 363, pp. 490–498, Feb. 2016. doi: http://doi.org/10.1016/j.apsusc.2015.12.074. https://doi.org/10.1016/j.apsusc.2015.12... ]
MnFe₂O₄@CNT-N/GCE	Caffeine	1.0 × 10⁻⁶ to 1.1 × 10⁻³ M	3 0.83 × 10⁻⁶ M	–	[¹²⁴[124] FERNANDES, D.M., SILVA, N., PEREIRA, C., et al., “MnFe2O4@CNT-N as novel electrochemical nanosensor for determination of caffeine, acetaminophen and ascorbic acid”, Sensors and Actuators. B, Chemical, v. 218, pp. 128–136, Oct. 2015. doi: http://doi.org/10.1016/j.snb.2015.05.003. https://doi.org/10.1016/j.snb.2015.05.00... ]
SWNTs aptasensor	Cocaine	0.1–10 nM	105 pM	Detected cocaine spiked in rat serum with limit of detection of 136 pM	[¹²⁵[125] TAGHDISI, S.M., DANESH, N.M., EMRANI, A.S., et al., “A novel electrochemical aptasensor based on single-walled carbon nanotubes, gold electrode and complimentary strand of aptamer for ultrasensitive detection of cocaine”, Biosensors & Bioelectronics, v. 73, pp. 245–250, Nov. 2015. doi: http://doi.org/10.1016/j.bios.2015.05.065. PubMed PMID: 26086444. https://doi.org/10.1016/j.bios.2015.05.0... ]
PANI-β-CD/fMWCNT/GCE	Cocaine	10–80 μM	1.02 μM	The sensor was used to analyze seized street samples of cocaine and showed good agreement with an HPLC reference method. Recoveries of 70-71% were obtained.	[¹²⁶[126] GARRIDO, J.M.P.J., BORGES, F., BRETT, C.M.A., et al., “Carbon nanotube ß-cyclodextrin-modified electrode for quantification of cocaine in seized street samples”, Ionics, v. 22, n. 12, pp. 2511–2518, Dec. 2016. doi: http://doi.org/10.1007/s11581-016-1765-3. https://doi.org/10.1007/s11581-016-1765-... ]
poly(MAA)/MWCNT/β-CD-GCE	Cocaine	12.2 to 200.0 μM	3.6 μM	The method was applied to determine COC in seized street samples and showed good accuracy compared to HPLC-DAD. Recoveries between 100.3–101.9% were obtained.	[¹²⁷[127] CAPELARI, T.B., DE CÁSSIA MENDONÇA, J., DA ROCHA, L.R., et al., “Synthesis of novel poly(methacrylic acid)/ß-cyclodextrin dual grafted MWCNT-based nanocomposite and its use as electrochemical sensing platform for highly selective determination of cocaine”, Journal of Electroanalytical Chemistry (Lausanne, Switzerland), v. 880, pp. 114791, Jan. 2021. doi: http://doi.org/10.1016/j.jelechem.2020.114791. https://doi.org/10.1016/j.jelechem.2020.... ]

[1] Corresponding Author: Jiahui Yan, e-mail: yanjiahui1017@126.com

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Application and prospect of carbon nanomaterials in electroanalysis for detection of illicit drugs in sports

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