Mesostructured Silica-Coated Magnetic Nanoparticles to Extract Six Opium Alkaloids in Poppy Seeds Prior to Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry Analysis

Abstract

In recent years, health authorities have become increasingly concerned about preventing consumer exposure to opium alkaloids present in Papaver somniferum L. poppy seeds. In this study, a simple, rapid and efficient method has been optimised to determine all main opioids in poppy seeds (morphine, codeine, thebaine, papaverine, noscapine and oripavine) by UHPLC-QqQ-MS/MS. For this purpose, solid-liquid extraction (SLE) of samples was optimised and six magnetic adsorbent materials with a core of Fe3O4 coated with amorphous and mesostructured silica, both functionalised with octadecyl-silane or octyl-silane were characterised and evaluated for magnetic solid-phase extraction (MSPE). The material with the best results was non-functionalised mesostructured silica and, with it, the MSPE procedure was optimised. This method was validated and used to quantify six opioids in 14 edible seed samples (eleven poppy seeds and three seed mixes). Considerable amounts were found (1.5–249.0 mg/kg morphine, <0.2 µg/kg–45.8 mg/kg codeine, <2.4 µg/kg–136.2 mg/kg thebaine, <0.2 µg/kg–27.1 mg/kg papaverine, <0.2 µg/kg–108.7 mg/kg noscapine and <240 µg/kg–33.4 mg/kg oripavine), exceeding maximum limits established in some EU countries and the reference level of morphine in the EU. Furthermore, in some commercial samples for human consumption, inadequate labelling was found because significant amounts of alkaloids were detected even though Papaver rhoeas L. seeds were declared on the product label.

Evaluation of Thermal Degradation of Tropane and Opium Alkaloids in Gluten-Free Corn Breadsticks Samples Contaminated with Stramonium Seeds and Baked with Poppy Seeds under Different Conditions

“…Consequently, to separate the nine alkaloids, different mobile phases were evaluated in this work. In order to obtain good separation (resolution, Rs ≥ 1.5) and peak shape (peak asymmetry factor, As = 1), the effect of the formic acid [ 11 , 14 , 26 , 27 ] or trifluoroacetic acid [ 25 , 28 ] concentration in the mobile phase was evaluated. The concentration of both acids was tested in the range of 0.05 to 0.2% ( v / v ).…”

“…A review of the extraction protocols in the literature shows that methanol [ 25 ], acidified methanol [ 21 ], acidified water [ 37 , 38 ], and a mixture of solvents [ 14 , 20 , 39 , 40 ] are used to extract OAs from both poppy seeds and foodstuffs. TAs can be extracted from foods using acidified water [ 11 ] or a mixture of solvents [ 22 , 41 , 42 ].…”

“…Based on these previous papers, three types of extraction solvents were evaluated in our study: methanol/water (2/1, v / v ) with 0.5% acetic acid, acetonitrile/water (80/20, v / v ) with 0.1% formic acid and methanol with 0.1% acetic acid. In addition, according to the study of Casado-Hidalgo et al [ 14 ] two successive extractions with 10 mL of solvent were considered sufficient to extract the compounds of interest. Breadsticks samples prepared with TAs-free corn flour containing OAs-free chia seeds were used in order to avoid the presence of both types of toxic alkaloids in the sample.…”

“…This is often due to the cereal cleaning practices, which are not always effective for weed-seeds removal. On the other hand, some seeds used in the preparation of bakery products, such as poppy seeds, have been shown to contain high amounts of opium alkaloids (OAs) [ 14 ]. OAs represent different classes of compounds isolated from Papaver somniferum L. This plant contains more than 40 individual OAs, the main ones being morphine, codeine, thebaine, papaverine, and noscapine, which can be used as analgesics and narcotics, cough suppressant, muscle relaxant, or as an anti-tumour agent [ 15 ].…”

Occurrence and Chemistry of Tropane Alkaloids in Foods, with a Focus on Sample Analysis Methods: A Review on Recent Trends and Technological Advances

“…Recently, OMSs are being highly used in different compounds such as xenobiotics [52], process contaminants [53] and natural toxins [14,54], and they can also be applied in different sorbent-based techniques such as SPE, dSPE or MSPE, among others [55]. In this sense, SBA-15 has been the main hexagonal mesostructured silica employed as sorbent for sample preparation.…”