Rapid screening of illegal additives in functional food using desorption electrospray ionization mass spectrometry imaging.

Compounds such as Sildenafil, which bring potential health risks to consumers, have been illegally added to functional food. The public security department hopes to quickly screen for illegal additives. The quantity of seized samples is often large and their compositions are unknown; it is necessary to screen the unknown samples qualitatively and sometimes quantitatively. In this paper, a new method for rapid screening of 39 common illegal additives in six categories of functional food based on DESI-MSI technology is proposed, and the DESI-MSI library is established, which can be used for exclusive and sensitive qualitative confirmation of suspicious samples. A new carrier material that can be used for rapid qualitative detection of solid sample is discovered. The samples require simple or even no pretreatment to carry out high-resolution imaging through the imaging function of DESI-MSI. The imaging results are clear and intuitive, and can achieve fast and high-throughput qualitative identification of illegally added compounds. This method has good linearity, accuracy, precision, and little effect of matrix, so it can roughly quantify the illegal additives in functional products. Twenty-one batches of unknown samples were detected by DESI-MSI, and the positive results were confirmed by LC-MS/MS (QQQ). The results showed that the DESI-MSI method was effective and reliable. DESI-MSI with self-made database is a promising method for rapid screening of illegal additives in functional food, which can be widely used in grass-roots police stations.

Rapid screening of illegal additives in functional food using atmospheric pressure solids analysis probe coupled to a portable mass spectrometer.

Pharmaceutical drugs like Sildenafil are illegally added to functional food such as nutritional supplements and herbal remedies to deliver drugs without a regular prescription to consumers. Rapid screening of illegal additives is desirable for the public security department. The seized samples are often large in number and unknown in composition; methods are needed for qualitative screening of unknown samples. Here, a new approach is presented based on atmospheric pressure solids analysis probe (ASAP) coupled with single-quadrupole mass spectrometer to rapidly screen 42 common illegal additives in six categories of functional food. The ASAP-MS method could be applied to solid or liquid sample analysis with a very simple pre-treatment and no LC chromatographic separation, using a home-built library; the identification of suspicious additives could be obtained rapidly. More importantly, the approach is sensitive enough for complex matrix samples like coffee samples. 21 batches of seized unknown samples were tested by the ASAP-MS, and the positive results were confirmed by LC-MS/MS(QQQ), indicating that the ASAP-MS method is effective and reliable. The ASAP-MS with home-built library is a promising method for rapid screening of illegal additives in functional food, which could be widely used in the grassroots police station that lack professional laboratory environment.

Validation of an UHPLC/DAD method for the determination of cannabinoids in seized materials: Analysis of 213 samples sold in Belgian CBD shops.

PURPOSE: Nowadays, (-)-cannabidiol (CBD) is gaining popularity for the treatment of various problems and can be found easily in many stores in Belgium. However, such product must comply with the law: if the total tetrahydrocannabinol (THC) content [(-)-Δ9-tetrahydrocannabinol + (-)-Δ9-tetrahydrocannabinolic acid A (THC-A)] is higher than 0.2%, it is considered as narcotic by the Belgian legislation. In this context, we have developed a method to quantify major cannabinoids (THC, THC-A, CBD, cannabidiolic acid, cannabigerolic acid, cannabigerol and cannabinol) in plant material. METHODS: After drying, a liquid-liquid extraction was performed on plant materials, followed by dilutions. Extracts were analyzed by ultra-high-performance liquid chromatography combined with a photodiode array detector. Mobile phases consisted of methanol and 0.1% formic acid in water applied in a 16-minute gradient mode. After validating the method, it was applied to 213 samples seized by the police in CBD shops. RESULTS: The method fulfilled the criteria in terms of specificity, calibration curve, precision, trueness and dosing range. Total THC content ranged from 0.14 to 1.17% (median 0.38%) with 110 samples exceeding the Belgian legal threshold of 0.2%. The amounts measured in the samples varied greatly, some were 6 times below the amount labelled on the packaging, others showed a concentration 4 times higher than stated on the package. Same strain also showed concentration differences from shop to shop. CONCLUSION: Our method was successfully validated and applied to samples seized in CBD shops. Half of the products exceeded the Belgian legal threshold. THC and CBD concentrations discrepancies showed that products sold in CBD shops are not pharmaceutical grade.

Attribution of fentanyl analogue synthesis routes by multivariate data analysis of orthogonal mass spectral data.

Chemical attribution signatures (CAS) can be used to obtain useful forensic information and evidence from illicit drug seizures. A CAS is typically generated using hyphenated chemical analysis techniques and consists of a fingerprint of the by-products and additives present in a sample. Among other things, it can provide information on the sample's origin, its method of production, and the sources of its precursors. This work investigates the possibility of using multivariate CAS analysis to identify the synthetic methods used to prepare seized fentanyl analogues, independently of the analogues' acyl derivatization. Three chemists working in two labs synthesized three different fentanyl analogues, preparing each one in duplicate by six different routes. The final collection of analogues (96 samples) and two intermediates (16 + 32 samples) were analysed by GC-MS and UHPLC-HRMS, and the resulting analytical data were used for multivariate modelling. Independently of analogue structure, the tested fentanyls could be classified based on the method used in the first step of their synthesis. The multivariate model's ability to classify unknown samples was then evaluated by applying it to six new fentanyl analogues. Additionally, seized fentanyl samples was analysed and classified by the model.

Evaluation of a low-cost portable near-infrared spectrophotometer for in situ cocaine profiling.

The potential of a low-cost (∼US$ 1000) portable near-infrared (NIR) spectrophotometer for in situ characterization of seized cocaine samples was evaluated. A set of 240 samples of cocaine seized in several regions and cities across Brazil by its federal police was employed in this study. These samples were previously analyzed by chromatography at the Forensic Chemistry Laboratory of the National Institute of Criminalistics in Brasília-DF for the contents of several constituents to chemically characterize the samples. A low-cost NanoNIR spectrophotometer (Texas instruments) was used to acquire the NIR spectra of the samples in the range 900-1700 nm. The spectra set was treated by the second derivative to construct and validate multivariate regression (Partial Least Square - PLS) and classification (software independent modeling of class analogy - SIMCA) models aiming to characterize the samples. Consequently, an informative toll for objective decision making could be used by the police agents to produce immediate answers to forensic questions raised at the point of seizing. Among those questions the most relevant are: does the seized sample contain cocaine? what is the cocaine form? what is its content? is the sample adulterated and/or diluted? what is the content of adulterant? is the sample significantly adulterated and/or diluted? what is the degree of oxidation of the cocaine? The results of this work allow to propose a NIR/chemometrics based analytical protocol providing fast answers to these questions with satisfactory confidence level for the purpose of reliably screen the seized samples.