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1 This work has shown that nanoMIPs coupled with an EIS sensor platform can be used to detect cocaine at trace levels. To the best of our knowledge, a sensor based on nanoMIPs and EIS has not been reported previously.
ROBERTA D'AURELIO
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D’aurelio, R.; Chianella, I.; Goode, J.A.; Tothill, I.E. Molecularly Imprinted Nanoparticles Based Sensor. Encyclopedia. Available online: https://encyclopedia.pub/entry/960 (accessed on 16 April 2024).
D’aurelio R, Chianella I, Goode JA, Tothill IE. Molecularly Imprinted Nanoparticles Based Sensor. Encyclopedia. Available at: https://encyclopedia.pub/entry/960. Accessed April 16, 2024.
D’aurelio, Roberta, Iva Chianella, Jack A. Goode, Ibtisam E. Tothill. "Molecularly Imprinted Nanoparticles Based Sensor" Encyclopedia, https://encyclopedia.pub/entry/960 (accessed April 16, 2024).
D’aurelio, R., Chianella, I., Goode, J.A., & Tothill, I.E. (2020, May 29). Molecularly Imprinted Nanoparticles Based Sensor. In Encyclopedia. https://encyclopedia.pub/entry/960
D’aurelio, Roberta, et al. "Molecularly Imprinted Nanoparticles Based Sensor." Encyclopedia. Web. 29 May, 2020.
Molecularly Imprinted Nanoparticles Based Sensor
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This entry is adapted from the peer-reviewed paper 10.3390/bios10030022

The development of a sensor based on molecularly imprinted polymer nanoparticles (nanoMIPs) and electrochemical impedance spectroscopy (EIS) for the detection of trace levels of cocaine is described in this paper. NanoMIPs for cocaine detection, synthesized using a solid phase, were applied as the sensing element. The nanoMIPs were first characterized by Transmission Electron Microscopy (TEM) and Dynamic Light Scattering and found to be ~148.35 ± 24.69 nm in size, using TEM. The nanoMIPs were then covalently attached to gold screen-printed electrodes and a cocaine direct binding assay was developed and optimized, using EIS as the sensing principle. EIS was recorded at a potential of 0.12 V over the frequency range from 0.1 Hz to 50 kHz, with a modulation voltage of 10 mV. The nanoMIPs sensor was able to detect cocaine in a linear range between 100 pg mL-1 and 50 ng mL-1 (R2 = 0.984; p-value = 0.00001) and with a limit of detection of 0.24 ng mL-1 (0.70 nM). The sensor showed no cross-reactivity toward morphine and a negligible response toward levamisole after optimizing the sensor surface blocking and assay conditions. The developed sensor has the potential to offer a highly sensitive, portable and cost-effective method for
cocaine detection.

cocaine drugs of abuse electrochemical impedance spectroscopy molecularly imprinted polymer nanoparticles EIS sensor

1. Introduction

Cocaine is classified as a central nervous system stimulant and is the most abused drug in the world, after cannabis. With over 655 tons detained yearly, cocaine is also one of the most seized illicit drugs worldwide [1] and is one of the major recreational drugs illegally trafficked in European countries, where there are more than 17.5 million users [2]. Illicit-drugs-related crimes are of huge concern due to the burden on law enforcement agencies (LEAs) and healthcare systems, with associated social and economic problems.

2. Detection

To detect, control and manage drugs of abuse trafficking, LEAs make use of the powerful olfactory system of “sniffer dogs”. After an appropriate training, dogs are able to “smell and detect” very low concentrations (in the range of ppb) of illicit drugs concealed in various items, including packages and containers [3][4]. However, sniffer dogs can be prone to work fatigue and can be deceived by handlers [5]. Forensic chemistry can provide evidence on whether a suspected substance contains illegal drugs by means of reproducible scientific methods, thus providing unequivocal evidence of the drug-related offence [6]. Generally, suspected samples (either biological or environmental) are analyzed by presumptive and confirmatory tests. The former comes as rapid detection kits or devices, which are mainly screening tests indicating whether illegal drugs may be present or not [7]. Currently, onsite screening methods rely on Ion Mobility Spectroscopy (IMS) [8], competitive inhibition immunoassay [9] and colorimetric tests [7]. Nevertheless, these methods provide only qualitative or semi-quantitative results; they are prone to false-positive and negative results and many require trained personnel for operation. Confirmatory analyses are currently performed in accredited ISO 17025 laboratories, through several complex procedures and expensive analytical tools, such as GC–MS and LC-MS [10].

3. Sensor

Therefore, there is a need for new technologies that can provide fast screening tests with a high level of sensitivity and specificity. These technologies may speed up the investigative activities, thus reducing the false-positive/false-negative rate and, hence, confining the demand of confirmatory tests only on truly positive samples. Hence, the aim of this work was to develop a rapid and specific sensor able to detect cocaine at trace levels, to be used in diverse onsite testing scenarios, to tackle cocaine trafficking. While it is difficult to reproduce the complexity of the olfactory systems, electrochemical biosensors can offer an analogous way to transform the binding of the analyte to its sensing receptor into an electrical signal. Examples of electrochemical sensors for cocaine detection using aptamers or biomolecules have already been described in the literature [11][12][13]. Among all the electrochemical techniques available, in recent years, electrochemical impedance spectroscopy (EIS) has gained attention due to its ability of detecting the target molecules at very low concentrations. Compared to amperometry and potentiometry, EIS is able to detect minimal changes at the sensor surface boundaries, thus leading to several advantages, such as a wide linear range, low limits of detection and direct assay mode. The method can also preserve the sample for further confirmatory analysis [14][15]. The basic principle behind EIS is the electrical impedance, which indicates the resistance that an electrical circuit presents to the flow of an alternating current (AC), generated by applying a small alternating voltage (AV) [16]. EIS can be performed with or without a redox probe (redox couple), such as potassium ferricyanide/ferrocyanide ([Fe(CN)6]3−/4−), added to the solution. When the redox probe is present, faradic current is gathered, thus leading to faradic EIS sensor. In this case, the resistance charge transfer (Rct) electrical element is usually affected by the events occurring at the electrode surface, such as the binding between a sensing receptor and its target [17].

In order to obtain a sensor suitable for onsite testing, it is highly desirable to employ stable and robust sensing elements. Previous works have demonstrated that the use of molecularly imprinted polymers in electrochemical sensing can result in robust, sensitive and specific diagnostic systems [18][19][20]. Particularly, molecularly imprinted nanoparticles (nanoMIPs), prepared using a solid phase, have shown to be a powerful and robust mimic of antibodies in sensors and assays [21][22][23], while providing convenient and animal-free synthesis. NanoMIPs have shown to be stable at a wide range of temperature and to possess a long shelf-life, with no need of refrigeration and preservation [22][24]. As such, nanoMIPs are the ideal receptor candidate for sensors that have to operate in unpredictable environmental conditions, which might contain denaturing agents and degrading enzymes capable of denaturing bio-derived receptors (protein, antibodies and aptamers).

Therefore, nanoMIPs and EIS were applied in this work for the first time to develop a highly sensitive and specific affinity sensor to detect traces of cocaine. The resulting nanoMIPs EIS sensor was able to detect cocaine in the low nM range, demonstrating potential application as a cheap and portable analytical tool to use in investigative activities of illicit drugs trafficking.

References

  1. UNODC. World Drug Report 2016; United Nations Office on Drugs and Crime: Vienna, Austria, 2016.
  2. EMCDDA. European Drug Report 2017: Trends and Developments; European Monitoring Centre for Drugs and Drug Addiction: Lisbon, Portugal, 2017.
  3. Michelle M. Cerreta; Kenneth G. Furton; An assessment of detection canine alerts using flowers that release methyl benzoate, the cocaine odorant, and an evaluation of their behavior in terms of the VOCs produced. Forensic Science International 2015, 251, 107-114, 10.1016/j.forsciint.2015.03.021.
  4. Tadeusz Jezierski; Ewa Adamkiewicz; Marta Walczak; Magdalena Sobczyńska; Aleksandra Górecka-Bruzda; John Ensminger; Eugene Papet; Efficacy of drug detection by fully-trained police dogs varies by breed, training level, type of drug and search environment. Forensic Science International 2014, 237, 112-118, 10.1016/j.forsciint.2014.01.013.
  5. Olivia Leitch; Alisha Anderson; K. Paul Kirkbride; Chris Lennard; Biological organisms as volatile compound detectors: A review. Forensic Science International 2013, 232, 92-103, 10.1016/j.forsciint.2013.07.004.
  6. UNODC. Recommended Methods for the Identification and Analysis of Cocaine in Seized Materials; United Nations Office on Drugs and Crime: Vienna, Austria, 2012.
  7. Lane Harper; Jeff Powell; Em M. Pijl; An overview of forensic drug testing methods and their suitability for harm reduction point-of-care services.. Harm Reduction Journal 2017, 14, 52, 10.1186/s12954-017-0179-5.
  8. Raquel Cumeras; E. Figueras; C. E. Davis; J. I. Baumbach; Isabel Gràcia; Review on ion mobility spectrometry. Part 2: hyphenated methods and effects of experimental parameters.. The Analyst 2015, 140, 1391-410, 10.1039/c4an01101e.
  9. F Musshoff; Eva Große Hokamp; Ulrich Bott; B. Madea; Performance evaluation of on-site oral fluid drug screening devices in normal police procedure in Germany. Forensic Science International 2014, 238, 120-124, 10.1016/j.forsciint.2014.02.005.
  10. Angelo Cecinato; Catia Balducci; Mattia Perilli; Illicit psychotropic substances in the air: The state-of-art. Science of The Total Environment 2016, 539, 1-6, 10.1016/j.scitotenv.2015.08.051.
  11. Lukasz Poltorak; Ernst J.R. Sudhölter; Marcel De Puit; Electrochemical cocaine (bio)sensing. From solid electrodes to soft junctions. TrAC Trends in Analytical Chemistry 2019, 114, 48-55, 10.1016/j.trac.2019.02.025.
  12. Ahad Mokhtarzadeh; Jafar Ezzati Nazhad Dolatabadi; Khalil Abnous; Miguel De La Guardia; Mohammad Ramezani; Nanomaterial-based cocaine aptasensors. Biosensors and Bioelectronics 2015, 68, 95-106, 10.1016/j.bios.2014.12.052.
  13. Seyed Mohammad Taghdisi; Noor Mohammad Danesh; Ahmad Sarreshtehdar Emrani; Mohammad Ramezani; Khalil Abnous; A novel electrochemical aptasensor based on single-walled carbon nanotubes, gold electrode and complimentary strand of aptamer for ultrasensitive detection of cocaine. Biosensors and Bioelectronics 2015, 73, 245-250, 10.1016/j.bios.2015.05.065.
  14. Jack Goode; G. Dillon; P. A. Millner; The development and optimisation of nanobody based electrochemical immunosensors for IgG. Sensors and Actuators B: Chemical 2016, 234, 478-484, 10.1016/j.snb.2016.04.132.
  15. Trong Binh Tran; Sang Jun Son; Junhong Min; Nanomaterials in label-free impedimetric biosensor: Current process and future perspectives. BioChip Journal 2016, 10, 318-330, 10.1007/s13206-016-0408-0.
  16. Jose Muñoz; Raquel Montes; Mireia Baeza; Trends in electrochemical impedance spectroscopy involving nanocomposite transducers: Characterization, architecture surface and bio-sensing. TrAC Trends in Analytical Chemistry 2017, 97, 201-215, 10.1016/j.trac.2017.08.012.
  17. Flávio C.B. Fernandes; Adriano Santos; Denise C. Martins; Márcio Sousa Góes; Paulo Roberto Bueno; Comparing label free electrochemical impedimetric and capacitive biosensing architectures. Biosensors and Bioelectronics 2014, 57, 96-102, 10.1016/j.bios.2014.01.044.
  18. Rijun Gui; Huijun Guo; Hui Jin; Preparation and applications of electrochemical chemosensors based on carbon-nanomaterial-modified molecularly imprinted polymers. Nanoscale Advances 2019, 1, 3325-3363, 10.1039/c9na00455f.
  19. Chunju Zhong; Bin Yang; Xinxin Jiang; Jianping Li; Current progress of nanomaterials in molecularly imprinted electrochemical sensing.. Critical Reviews in Analytical Chemistry 2017, 48, 1-18, 10.1080/10408347.2017.1360762.
  20. Rijun Gui; Hui Jin; Huijun Guo; Zonghua Wang; Recent advances and future prospects in molecularly imprinted polymers-based electrochemical biosensors. Biosensors and Bioelectronics 2018, 100, 56-70, 10.1016/j.bios.2017.08.058.
  21. M.J. Abdin; Zeynep Altintas; Ibtisam E. Tothill; Z. Altıntaş; In silico designed nanoMIP based optical sensor for endotoxins monitoring. Biosensors and Bioelectronics 2015, 67, 177-183, 10.1016/j.bios.2014.08.009.
  22. Iva Chianella; Antonio Guerreiro; Ewa Moczko; J. Sarah Caygill; Elena V. Piletska; Isabel M. Perez De Vargas Sansalvador; Michael J Whitcombe; Sergey A. Piletsky; Direct Replacement of Antibodies with Molecularly Imprinted Polymer Nanoparticles in ELISA—Development of a Novel Assay for Vancomycin. Analytical Chemistry 2013, 85, 8462-8468, 10.1021/ac402102j.
  23. Elisabetta Mazzotta; Antonio Turco; Iva Chianella; Antonio Guerreiro; Sergey A. Piletsky; Cosimino Malitesta; Solid-phase synthesis of electroactive nanoparticles of molecularly imprinted polymers. A novel platform for indirect electrochemical sensing applications. Sensors and Actuators B: Chemical 2016, 229, 174-180, 10.1016/j.snb.2016.01.126.
  24. Serena Ambrosini; Selim Beyazit; Karsten Haupt; Bernadette Tse Sum Bui; Solid-phase synthesis of molecularly imprinted nanoparticles for protein recognition. Chemical Communications 2013, 49, 6746, 10.1039/c3cc41701h.
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Subjects: Nanoscience & Nanotechnology; Biotechnology & Applied Microbiology
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Roberta D’Aurelio
,
Iva Chianella
,
Jack A. Goode
,
Ibtisam E. Tothill
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Revisions: 4 times (View History)
Update Date: 02 Nov 2020
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