Comparison of direct analysis in real-time mass spectrometry, atmospheric solids analysis probe-mass spectrometry, and ion mobility spectrometry for ensuring food safety by rapid screening of poppy seeds.

The opium poppy (Papaver somniferum) is a global commercial crop that has been historically valued for both medicinal and culinary purposes. Naturally occurring opium alkaloids including morphine, codeine, thebaine, noscapine, and papaverine are found primarily in the latex produced by the plant. If the plant is allowed to fully mature, poppy seeds that do not contain the opium alkaloids will form within the pods and may be used in the food industry. It is possible for the seeds to become contaminated with alkaloids by the latex during harvesting, posing a potential health risk for consumers. In the USA, there have been more than 600 reported adverse events including 19 fatalities that may be linked to the consumption of a contaminated poppy-containing product such as home-brewed poppy seed tea. Unwashed poppy seeds and pods may be purchased over the Internet and shipped worldwide. The Forensic Chemistry Center, US Food and Drug Administration (FDA) has evaluated several mass spectrometers (MS) capable of rapid screening to be used for high-throughput analysis of samples such as poppy seeds. These include a direct analysis in real-time (DART) ambient ionization source coupled to a single-quadrupole MS, an atmospheric solids analysis probe (ASAP) ionization source coupled to the same MS, and ion mobility spectrometers (IMS). These instruments have been used to analyze 17 poppy seed samples for the presence of alkaloids, and the results were compared to data obtained using liquid chromatography with mass spectral detection (LC-MS/MS). Results from the 17 poppy seed samples indicate that the DART-MS, ASAP-MS, and IMS devices detect many of the same alkaloids confirmed during the LC-MS/MS analyses, although both the false-positive and false-negative rates are higher, possibly due to the non-homogeneity of the samples and the lack of chromatographic separation.

Evaluation of "Toolkit" consisting of handheld and portable analytical devices for detecting active pharmaceutical ingredients in drug products collected during a simultaneous nation-wide mail blitz.

A "toolkit" consisting of a handheld Raman spectrometer equipped with a 1064 nm laser, a portable Fourier transform infrared (FT-IR) spectrometer and a portable direct analysis in real-time mass spectrometer (DART-MS) was employed in a laboratory setting to examine 82 representative products collected during a nationwide mail blitz for the presence of APIs. These results were compared to those obtained using laboratory-based methods; 8 of the products were not found to contain APIs and 74 of the products were found to contain a total of 88 APIs (65 of the 88 APIs were unique). The individual performance of each device and combined performance of the three-device toolkit were evaluated with regard to true positives, true negatives, false positives and false negatives. Using this toolkit, 81 (92.0 %) of the APIs were detected by at least one technique and 47 (64.8 %) of the APIs were detected by at least two techniques. Seven false negatives (8.0 %) were encountered and while the toolkit yielded 12 false positives, no false positives were detected by more than one technique. Overall, this study demonstrated that when the toolkit detects an API using two or more devices, the results are as reliable as those generated by a full-service laboratory.

Evaluation of four field portable devices for the rapid detection of mitragynine in suspected kratom products.

The development of a method for the rapid screening of food and drug products for constituents such as mitragynine, the most abundant alkaloid found in Mitragyna speciosa (kratom) plant leaves, has become increasingly important. The use of kratom is said to produce stimulant or narcotic effects and poses risks of addiction, abuse, and dependence, much like other opioids. Direct Analysis in Real Time with thermal desorption mass spectrometry (DART-TD-MS), hand-held mass spectrometry, portable ion mobility spectrometry (IMS), and portable Fourier-transform infrared spectroscopy (FT-IR) were each evaluated as field-deployable screening techniques for the detection of mitragynine in food and drug products. These devices offer the potential for rapid, early detection of mitragynine in suspect products entering the United States through international mail facilities and other ports of entry. Ninety-six kratom products, including capsules, bulk powder, and bulk plant material, were analyzed by either direct sampling of the solid material or by solvent extraction. True and false positive and negative results are reported, based on comparison to results from qualitative screening using gas chromatography with mass spectral detection (GC-MS), liquid chromatography with mass spectral detection (LC-MS), and/or quantitative screening using high-performance liquid chromatography with ultraviolet detection (HPLC-UV), with a discussion of the assessment of each technique for use in the field. Each device demonstrated attributes that would be favorable for use in screening of suspected mitragynine-containing products at places like ports of entry, and simultaneous deployment of two or more of these devices as part of a workflow would be the most effective for rapid screening of these products. This combination of rapid screening orthogonal techniques suited to a non-laboratory environment will allow onsite destruction of products found to contain mitragynine.

Semi-quantitative determination of designer steroids by high-performance liquid chromatography with ultraviolet detection in the absence of reference material.

New designer steroids are continually being encountered in dietary supplements that claim to increase muscle mass, but quantitative analysis of such ingredients is challenging due to the availability, quality, or cost of commercial reference materials. Although standard reference material typically becomes available for these emerging compounds, laboratories often face the challenge of finding properly certified materials from accredited suppliers, due to traceability requirements. Several of these designer steroids have been isolated and identified using multiple structural elucidation tools. Structural characteristics of these compounds of interest were evaluated and molar absorptivity data was collected and compared to several readily available steroid standards using ultraviolet/visible spectroscopy. This approach was used to find suitable compounds for use as surrogate reference materials in the semi-quantitative determination of two designer steroids, 1-dehydroepiandrosterone (1-androsterone) and 6ß-chloro-4-androsten-17ß-ol-3-one (6ß-chlorotestosterone). Laboratory-fortified matrix samples and dietary supplement samples were analyzed using this method for the estimation of 1-androsterone and 6ß-chlorotestosterone by HPLC-UV. Assay values obtained for the estimation of 1-androsterone in a dietary supplement sample using a prasterone or dehydroepiandrosterone (DHEA) standard curve were 100% of those obtained using a 1-androsterone reference standard, once it became commercially available. Estimations for 6ß-chlorotestosterone in laboratory-fortified matrix samples using a testosterone standard curve were 92%-93% of those obtained using isolated 6ß-chlorotestosterone as "reference material."

Identification of the anabolic steroid 6ß-chlorotestosterone in a dietary supplement.

Capsules that were labeled to be performance-enhancing dietary supplements obtained during an investigation were found to contain an unrecognized steroid-like substance. This compound was isolated by liquid chromatography (LC) fraction collection and characterized using several qualitative analytical techniques, including ultraviolet (UV) spectroscopy, gas chromatography-mass spectrometry (GC-MS), liquid chromatography-high resolution accurate mass-mass spectrometry (LC-HRAM-MS), as well as 1 H, 13 C, and two-dimensional nuclear magnetic resonance (NMR) spectrometry. This multi-technique analytical approach was used to identify the designer steroid as 6ß-chloro-4-androsten-17ß-ol-3-one (6ß-chlorotestosterone), an analog of testosterone about which little has been published.

Forensic Drug Identification, Confirmation, and Quantification Using Fully Integrated Gas Chromatography with Fourier Transform Infrared and Mass Spectrometric Detection (GC-FT-IR-MS).

This manuscript is a continuation of a recent study that described the use of fully integrated gas chromatography with direct deposition Fourier transform infrared detection and mass spectrometric detection (GC-FT-IR-MS) to identify and confirm the presence of sibutramine and AB-FUBINACA. The purpose of the current study was to employ the GC-FT-IR portion of the same instrument to quantify these compounds, thereby demonstrating the ability to identify, confirm, and quantify drug substances using a single GC-FT-IR-MS unit. The performance of the instrument was evaluated by comparing quantitative analytical figures of merit to those measured using an established, widely employed method for quantifying drug substances, high performance liquid chromatography with ultraviolet detection (HPLC-UV). The results demonstrated that GC-FT-IR was outperformed by HPLC-UV with regard to sensitivity, precision, and linear dynamic range (LDR). However, sibutramine and AB-FUBINACA concentrations measured using GC-FT-IR were not significantly different at the 95% confidence interval compared to those measured using HPLC-UV, which demonstrates promise for using GC-FT-IR as a semi-quantitative tool at the very least. The most significant advantage of GC-FT-IR compared to HPLC-UV is selectivity; a higher level of confidence regarding the identity of the analyte being quantified is achieved using GC-FT-IR. Additional advantages of using a single GC-FT-IR-MS instrument for identification, confirmation, and quantification are efficiency, increased sample throughput, decreased consumption of laboratory resources (solvents, chemicals, consumables, etc.), and thus cost.