The identification of fentanyl, a main culprit in opioid overdose deaths, has become critical. Whereas Raman spectroscopy is an effective tool for detecting illicit drugs, the weak intensity of Raman scattering can make it difficult to distinguish trace materials. This shortcoming is addressed by surface-enhanced Raman spectroscopy (SERS), which produces strong signal enhancements when target compounds are near metal nanoparticles. This work examines the use of a paper-based substrate impregnated with silver nanoparticles for the detection of trace quantities of fentanyl alone and as an adulterant in heroin. In addition, intensity ratios of diagnostic peaks associated with each substance were fitted to a Langmuir isotherm calibration model and used for the quantitative analysis of fentanyl in heroin mixtures. Linearity was observed at <6% fentanyl, a significant finding that is consistent with concentrations found in drugs seized during law enforcement efforts. In addition, swabbing with these paper-based SERS substrates facilitated the recovery of fentanyl from surfaces, showing this to be applicable for crime scene investigations. However, assessment using the calibration model proved difficult for swabbed samples. Overall, this work demonstrates a potentially simple and sensitive technique for the forensic analysis and quantitation of fentanyl in trace amounts.
We present a new method based on surface-enhanced Raman scattering (SERS) for the nondestructive identification of organic colorants in objects whose value or function precludes sampling, such as drawings, prints, historic and archeological textiles, handwritten or printed documents, and forensic evidence. A bead of a polymer hydrogel loaded with a solution containing water, an organic solvent, and a chelating agent is used to extract minimal amounts of the colorants from the work of art for SERS analysis. Using a gel as a medium for the solvent mixture confines its action only to the areas of the work of art covered by the gel bead. The gel bead is then removed from the work of art, covered with a drop of Ag colloid, and examined with a Raman microscope. Transfer of the dye from the substrate to the gel does not require removing a sample from the work of art, therefore preserving the physical integrity of the object. Spectrophotometric color measurements confirm that color change is below the limit perceivable by a human observer. Finally, the size of the polymer bead can be reduced to a fraction of a millimeter in order to further minimize any impact on the work of art, without detriment to the effectiveness of the method. The technique has been successfully used for the analysis of a mordant dye on the 15th century Netherlandish tapestry, "The Hunt for the Unicorn", and of a synthetic lake pigment on a Meiji period Japanese woodblock print.
: We obtain the normal Raman and surface‐enhanced Raman spectrum of three controlled substances: morphine, codeine, and hydrocodone. The spectra are assigned with the aid of density functional theory. Because of rather intense fluorescence, normal Raman spectra suffer from poor signal‐to‐noise, even when differential subtraction techniques are employed. On the other hand, surface enhancement by Ag nanoparticles both enhances the Raman signal and suppresses the fluorescence, enabling far more sensitive detection and identification. We also present a set of discriminant bands, useful for distinguishing the three compounds, despite the similarities in their structures.
We examine the normal Raman and the surface‐enhanced Raman spectra of fentanyl and carfentanil. As an aid in the assignment of the spectral lines, we present a density functional theory calculation. Although Raman spectroscopy is a valuable analytic tool for the detection and identification of molecular species, it is a weak effect and requires specialized equipment for detection of trace samples. We therefore turn to surface‐enhanced Raman spectroscopy, which utilizes the large enhancement of the Raman signal endowed by proximity to silver or gold nanoparticles. The enhancement factor (EF) obtained in this experiment is ≥1.6 × 105. This points the way towards future development of a simple and sensitive technique for the detection of analytes in trace quantities, particularly for wider application in forensic science.
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