The opioid crisis in the USA has resulted in over 702,000 overdose fatalities between 1999 and 2017 and can be attributed to over‐prescription of opioids and abuse of synthetic opioids in combination with other illicit drugs. A rapid and sensitive SERS method has been developed for trace detection of opioids including fentanyl, hydrocodone, oxycodone, and tramadol in low‐dosage suspect tablets using two different handheld Raman spectrometers equipped with 785 and 1064 nm lasers. The method involves a micro‐extraction procedure using 10% methanol in deionized water, followed by filtration and addition of colloidal silver and aqueous KBr, resulting in a mixture that can be measured directly via a glass vial. The lowest concentration (Cmin) of fentanyl, tramadol, oxycodone, and hydrocodone standards that yielded a positive match was 250 ng/ml, 5, 10, and 10 μg/ml using the 1064 nm laser device and 100 ng/ml, 1 μg/ml, 500 ng/ml, and 750 ng/ml using the 785 nm laser device, respectively. For the analysis of suspect tablets containing these opioids, the Cmin ranges between 5 and 75 µg/ml for 1064 nm laser device and 1 and 50 µg/ml for 785 nm laser device. The overall positive identification rate for all the opioids studied in the suspect counterfeit tablets analyzed ranged from 80% to 100%. The use of SERS for rapid chemical identification at remote sampling sites, such as international mail facilities (IMFs) and express courier hubs (ECHs), provides a rugged, simple, and practical method applicable for point‐of‐entry sampling and analysis.
A simple, quick, selective, sensitive, and effective field‐friendly method capable of being used by nonexperts has been developed for detecting mitragynine in Mitragyna speciosa (kratom) using surface‐enhanced Raman spectroscopy (SERS). Over 100 samples and blanks (known to be either positive or negative for the presence of mitragynine) were examined in duplicate using five identical handheld Raman spectrometers, which provided a data set of over 1,000 examinations. Based on the results of these analyses, the method yielded a true‐positive rate of 99.3%, a true‐negative rate of 97.9%, a false‐positive rate of 2.1%, and a false‐negative rate of 0.7%. The average minimum detectable concentration (Cm) of mitragynine that reproducibly yielded a match for one of the library spectra on all five instruments was determined to be 342 ng/mL (ppb). This Cm value is a conservative estimate considering that the extraction process was not fully optimized by this study, which was not necessary since the Cm value achieved was well below typical mitragynine concentrations in kratom (1.3–2.3%). The method is ideal (i) for prioritizing samples for additional testing using other more time‐consuming laboratory‐based techniques needed to detect and quantify mitragynine and (ii) for field use at international mail facility (IMF) satellite laboratories to help interdict kratom and prevent this dangerous product from reaching the U.S. supply chain.
This study describes the performance of handheld Raman devices for detecting one hundred opioids and related substances including fentanyl and several analogs. Using a single “parent” device, signatures (spectra) with excellent signal‐to‐noise ratios were generated using <5 mg of most compounds. The signatures were added to a method (library), which was electronically transferred to three “daughter” devices. The devices were able to discriminate different salt forms and isomers. On average, the daughter devices yielded a true‐positive rate of 97.3% for generating an alarm for opioids and were 93.3% effective for correctly identifying the opioid. The devices yielded true‐negative, false‐positive and false‐negative rates of 100%, 0%, and 2.7%, respectively, where false negatives were due to weak signal and fluorescence. These data demonstrate that the parent‐daughter electronic transfer method was successful and effective, which permits the ability to develop methods in the laboratory that can be seamlessly pushed out to field devices.
Analytes that co-elute and yield nearly identical electron ionization (EI) mass spectra, as well as analytes that yield non-specific EI fragmentation patterns, have been identified using fully integrated gas chromatography with direct deposit Fourier transform infrared detection and mass spectrometric detection (GC/FT-IR/MS). While the IR detector proved to be more selective for identifying analytes such as synthetic cannabinoids and weight loss drugs, it was limited by a relatively high detection limit of 8.4 parts per million (ppm) for non-targeted identification of sibutramine based on a single injection but was reduced to 840 parts per billion (ppb) for targeted identification of sibutramine by redepositing ten injections along the same track. The MS detector was less selective for identifying these analytes but yielded non-targeted and targeted detection limits of approximately 84 ppb and 8.4 ppb, respectively, which corresponded to a 100-fold advantage compared to the IR detector. Overall, the results of this study demonstrate that the advantages of each detector compensate for the limitations of the other, which allows a wider range of analytes and concentrations to be examined using a fully integrated GC/FT-IR/MS instrument compared to what can be examined using GC/IR or GC/MS independently. Not only does this approach reduce consumption of laboratory resources and time, it provides IR and MS information on the same sample, which is important for forensic analyses that require data from two or more orthogonal techniques to make an identification.
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