Pyrrolizidine alkaloids (PA) are secondary plant defense compounds and known pre-toxins when containing a 1,2-double bond. They are commonly produced by various plants and may thus be present in bee pollen which may be consumed by humans as food supplements. In this study, PA were determined in bee pollen samples from 57 locations in Southern Germany sampled by means of pollen traps in July 2019. Samples were analyzed by using palynological methodology and solid-phase extraction (SPE) followed by LC-MS/MS. In total, 52 pollen samples featured total pyrrolizidine alkaloids (ΣPA) with concentrations up to 48,000 ng/g bee pollen, while the N-oxides (NO) echinatine-NO and rinderine-NO clearly dominated. In contrast, the palynological analysis only detected 33 samples with pollen from PA-producing plants. Accordingly, the results showed that palynological analysis is not sufficient to determine PA in pollen. In addition, a risk assessment was followed to estimate the risk of the detected PA concentrations to humans.
Abstract Alkylresorcinols (5‐alkyl‐1,3‐dihydroxybenzenes) are amphiphilic phenolic lipid compounds that are abundant in cereals with highest contents in rye. Alkylresorcinols are suspected to show a wide range of favourable biological activities. For such and further testing, highly pure alkylresorcinol standards are required. Especially, purities >> 98% were partly difficult to obtain in the past. Here, we aimed to isolate the most abundant (saturated) alkylresorcinols from rye using countercurrent chromatography. To achieve very high purity, alkylresorcinol‐containing extract (∼7.14 g) of rye grains (cold extracts with cyclohexane/ethyl acetate (46/54, w/w)) were preparatively transesterified followed by a preparative hydrogenation. Countercurrent chromatography separation of ∼1 g hydrogenated and transesterified rye grain extract using the solvent system n ‐hexane–ethyl acetate–methanol–water (9:1:9:1, v/v/v/v) yielded 51.8 mg AR17:0, 77.4 mg AR19:0, 57.2 mg AR21:0, 28.8 mg AR23:0 and 11.5 mg AR25:0 with purities >99% in either case. The isolated alkylresorcinol homologues can be used for subsequent bioassays.
Abstract Trimethylsilyl‐enolethers of 5α‐ and 5β‐cholestan‐3‐on were investigated by gas chromatography and mass spectrometry. These derivatives are readily prepared and well suited for gas chromatographic analysis. In the mass spectrum they show fairly intense fragmentation, which appears to be characteristic for some structural elements in the surroundings of the functional group (excluding stereochemistry). This fragmentation may be useful for the structure elucidation of 3‐oxo‐steroids and related compounds. For comparison purposes the corresponding enolacetates were also investigated.
Abiotic and biotic transformation of toxaphene (camphechlor) results in the selective enrichment of recalcitrant congeners while other, less persistent compounds of technical toxaphene (CTTs) are degraded. Until now, there has been little knowledge on oxidation transformation of toxaphene. For instance, the existence of hydroxylated CTTs (OH-CTTs) in authentic environmental and food samples has not been proven. For this reason, we synthesized a mixture consisting of tetra- to heptachlorinated OH-CTTs and simplified it by countercurrent chromatography (CCC). Thus, 227 OH-CTTs were detected in the CCC fractions (12 tetra-, 117 penta-, 81 hexa-, and 17 heptachlorinated OH-CTTs), which was >50% more than detected before the fractionation. One CCC fraction consisting of only 18 OH-CTTs was used to develop a sample cleanup method which aimed to remove CTTs, isobaric PCBs, and sample matrix. The final cleanup procedure consisted of (i) gel permeation chromatography (GPC) and adsorption chromatography using (ii) deactivated and (iii) activated silica gel. Hence, up to 320 and 4350 μg/kg lipid weight of octa- and nonachlorinated CTTs were detected in four liver samples and adipose tissue of polar bears, respectively. Furthermore, the presence of one hexachlorinated OH-CTT isomer could be verified in the samples, which was about 1% of the octachlorinated CTTs determined in the liver samples.
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