Mahmut Şerif YILDIRIM, Necdet SAĞLAM, Hasan İLHAN, Ramazan AKÇAN, Uğur TAMER, Burcu GÜVEN

Surface enhanced Raman spectroscopy as a novel tool for rapid quantification of heroin and metabolites in saliva

Background: Heroin can be detected and quantified by certain analytical methods, however, forensic professionals and criminal laboratories study for cheaper and faster detection tools. Surface-enhanced Raman spectroscopy (SERS) rises as a possible alternative tool with its widening application spectra. There are few studies regarding Raman and SERS spectra of heroin and its metabolites, which are unfortunately controversial. In this study, we compared five different surfaces in order to find out more efficient Raman-active substrate for opiate detection and rapid quantification of heroin and its metabolites in saliva. Materials and methods: Morphine standard material was used to identify proper surface for SERS analysis of opiates. Heroin and its metabolites (morphine, morphine-3-ß-glucuronide and 6-monoacetyl morphine) were calibrated between 50 ppb and 500 ppm and quantified on AuNRs with signal enhancement of silver colloids in saliva. Raman microscope with a 785-nm laser source was used. Results and Conclusion: Obtained results showed that heroin and its metabolites can be detected and quantified in saliva samples using a SERS-based system. Additionally, the present study revealed that synergetic effect of a specific gold nano-surface with ability controlling liquid motion and silver nanoparticles increase band numbers and intensities. Therefore, we suggest a fast, accurate and cost-effective method to detect and quantify heroin in biological fluids.

PDF

___

1. Narayanswami K. UNODC-Bulletin on Narcotics-Parameters for determining the origin of illicit heroin samples. United Nations UNODC Bulletin 1985;49-62.
2. Cicero TJ, Ellis MS, Surratt HL, Kurtz SP. The changing face of heroin use in the United States. JAMA Psychiatry 2014;71 (7): 821-826.
3. Doty KC, McLaughlin G, Lednev IK. A Raman “spectroscopic clock” for bloodstain age determination: the first week after deposition. Analytical and Bioanalytical Chemistry 2016; 408 (15): 3993-4001.
4. McLaughlin G, Doty KC, Lednev IK. Discrimination of human and animal blood traces via Raman spectroscopy. Forensic Science International 2014; 238: 91-95.
5. Doty KC, Muro CK, Bueno J, Halámková L, Lednev IK. What can Raman spectroscopy do for criminalistics? Journal of Raman Spectroscopy 2016; 47 (1): 39-50.
6. Sikirzhytskaya A, Sikirzhytski V, McLaughlin G, Lednev IK. Forensic identification of blood in the presence of contaminations using Raman microspectroscopy coupled with advanced atatistics: effect of sand, dust, and soil. Journal of Forensic Sciences 2013; 58 (5): 1141-1148.
7. McLaughlin G, Lednev IK. Potential application of Raman spectroscopy for determining burial duration of skeletal remains. Analytical and Bioanalytical Chemistry 2011; 401 (8): 2511-2518.
8. Virkler K, Lednev IK. Raman spectroscopy offers great potential for the nondestructive confirmatory identification of body fluids. Forensic Science International 2008; 181 (1-3): e1e5.
9. Virkler K, Lednev IK. Analysis of body fluids for forensic purposes: From laboratory testing to nondestructive rapid confirmatory identification at a crime scene. Forensic Science International 2009; 188 (1-3): 1-17.
10. Bai S, Serien D, Hu A, Sugioka K. 3D microfluidic surfaceenhanced Raman spectroscopy (SERS) chips fabricated by all-femtosecond-laser-processing for real-time sensing of toxic substances. Advanced Functional Materials 2018; 28 (23): 1706262.
11. Farquharson S, Shende C, Sengupta A, Huang H, Inscore F. Rapid detection and identification of overdose drugs in saliva by surface-enhanced raman scattering using fused gold colloids. Pharmaceutics 2011;3 (3): 425-439.
12. Inscore F, Shende C, Sengupta A, Huang H, Farquharson S. Detection of drugs of abuse in saliva by surface-enhanced Raman spectroscopy (SERS). Applied Spectroscopy 2011; 65 (9): 1004-1008.
13. Yu B, Cao C, Li P, Mao M, Xie Q, Yang L. Sensitive and simple determination of zwitterionic morphine in human urine based on liquid-liquid micro-extraction coupled with surfaceenhanced Raman spectroscopy. Talanta 2018; 186: 427-432.
14. Meng J, Tang X, Zhou B, Xie Q, Yang L. Designing of ordered two-dimensional gold nanoparticles film for cocaine detection in human urine using surface-enhanced Raman spectroscopy. Talanta 2017; 164: 693-699.
15. Farquharson S, Gift A, Shende C, Inscore F, Ordway B et al. Surface-enhanced Raman spectral measurements of 5-fluorouracil in saliva. Molecules 2008; 13(10): 2608-2627.
16. Hays PA, Lurie IS. Quantitative analysis of adulterants in illicit heroin samples via reversed phase HPLC. Journal of Liquid Chromatography 1991; 14 (19): 3513-3517.
17. Rook EJ, Hillebrand MJX, Rosing H, Van Ree JM, Beijnen JH. The quantitative analysis of heroin, methadone and their metabolites and the simultaneous detection of cocaine, acetylcodeine and their metabolites in human plasma by high-performance liquid chromatography coupled with tandem mass spectrometry. Journal of Chromatography B 2005; 824 (1-2): 213-221.
18. Yilmaz M, Kuloglu HB, Erdogan H, Cetin SS, Yavuz MS et al. Light-driven unidirectional liquid motion on anisotropic gold nanorod arrays. Advanced Material Interfaces 2015; 2 (12):1500226.
19. Wen S, Zheng F, Shen M, Shi X. Synthesis of polyethyleneiminestabilized gold nanoparticles for colorimetric sensing of heparin.Colloids and Surfaces A Physicochemical and Engineering Aspects 2013; 419: 80-86.
20. Tamer U, Kanbeş Ç, Torul H, Ertaş N. Preparation, characterization and electrical properties of polyaniline nanofibers containing sulfonated cyclodextrin group. Reactive and Functional Polymers 2011; 71 (9): 933-937.
21. Leopold N, Lendl B. A New Method for Fast Preparation of Highly Surface-Enhanced Raman Scattering (SERS) Active Silver Colloids at Room Temperature by Reduction of Silver Nitrate with Hydroxylamine Hydrochloride. The Journal of Physical Chemistry B 2003; 107 (24): 5723-5727.
22. Dong R, Weng S, Yang L, Liu J. Detection and direct readout of drugs in human urine using dynamic surface-enhanced Raman spectroscopy and support vector machines. Analytical Chemistry 2015; 87 (5): 2937-2944.
23. De Oliveira Penido CAF, Pacheco MTT, Lednev IK, Silveira L. Raman spectroscopy in forensic analysis: identification of cocaine and other illegal drugs of abuse. Journal of Raman Spectroscopy 2016; 47 (1): 28-38.
24. Garrido JMPJ, Marques MPM, Silva AMS, Macedo TRA, Oliveira–Brett AM et al. Spectroscopic and electrochemical studies of cocaine-opioid interactions. Analytical and Bioanalytical Chemistry 2007; 388 (8): 1799-1808.
25. Rana V, Cañamares MV, Kubic T, Leona M, Lombardi JR. Surface-enhanced Raman spectroscopy for trace identification of controlled substances: morphine, codeine, and hydrocodone. Journal of Forensic Sciences 2011; 56 (1): 200-207.
26. Li P–W, Zhang J, Zhang L, Mo Y–J. Surface-enhanced Raman scattering and adsorption studies of morphine on silver island film. Vibrational Spectroscopy 2007; 49 (1): 2-6.
27. Hodges CM, Hendra PJ, Willis HA, Farley T. Fourier transform Raman spectroscopy of illicit drugs. Journal of Raman Spectroscopy 1989; 20 (11): 745-749.
28. Ryder AG, O’Connor GM, Glynn TJ. Identifications and quantitative measurements of narcotics in solid mixtures using near-IR Raman spectroscopy and multivariate analysis. Journal of Forensic Sciences 1999; 44 (5): 1013-1019.
29. Andreou C, Hoonejani MR, Barmi MR, Moskovits M, Meinhart CD. Rapid Detection of Drugs of Abuse in Saliva Using Surface Enhanced Raman Spectroscopy and Microfluidics. ACS Nano 2013;7 (8): 7157-7164.
30. Sägmüller B, Schwarze B, Brehm G, Trachta G, Schneider S. Identification of illicit drugs by a combination of liquid chromatography and surface-enhanced Raman scattering spectroscopy. Journal of Molecular Structure 2003; 661 (1): 279-290.
31. Izake EL. Forensic and homeland security applications of modern portable Raman spectroscopy. Forensic Science International 2010; 202 (1-3): 1-8.
32. Karinen R, Andersen JM, Ripel Å, Hasvold I, Hopen AB et al. Determination of heroin and its main metabolites in small sample volumes of whole blood and brain tissue by reversedphase liquid chromatography-tandem mass spectrometry. Journal of Analytical Toxicology 2009; 33 (7): 345-350.