Development of a High Performance Liquid Chromatography with Diode Array Detector (HPLC-DAD) Method for Determination of Biogenic Amines in Ripened Cheeses.

Biogenic amines (BAs) are organic, basic nitrogenous compounds formed during the decarboxylation of amino acids. A method for the determination of eight biogenic amines (tryptamine, 2-phenyletylamine, putrescine, cadaverine, histamine, tyramine, spermidine, spermine) in ripened cheeses was developed and validated. Cheese samples with the addition of internal standards were extracted with 0.2 M perchloric acid and pre-column derivatized with dansyl chloride at 60 °C for 15 min, purified with toluene and dried under a stream of nitrogen. The samples were analyzed using high performance liquid chromatography with diode array detector (HPLC-DAD). The method was validated with the BAs at three concentration levels: 50, 100, and 200 mg/kg, respectively. The obtained values of correlation coefficient (R2) ranged at 0.9997−0.9998 for all of compounds. The limits of detection (LOD) and quantification (LOQ) were in ranges 1.53−1.88 and 5.13−6.28 mg/kg, respectively. The recovery for all of biogenic amines ranged from 70 to 120% and the precision (RSDr) value were <20%. The validated method was applied to analysis of 35 real ripened cheese samples purchased in Poland.

Solid-phase extraction using octadecyl-bonded silica modified with photosynthetic pigments from Spinacia oleracea L. for the preconcentration of lead(II) ions from aqueous samples.

Spinacia oleracea L. extract was immobilized on an octadecyl-bonded silica surface to produce a new sorbent for the solid-phase extraction of trace amounts of metal ions from aqueous neutral samples. A measurement of the metal content has been performed by using graphite furnace atomic absorption spectroscopy. The affinity of the investigated bivalent metal cations for the modified sorbent are in the order: Pb(II) > Cu(II) > Ni(II) > Zn(II) ≈ Cd(II) ≈ Co(II). The quantum-chemically calculated chlorophyll-a-metal ion binding energies were consistent with the measured affinities of the corresponding metal ions to the investigated sorbent. The maximum sorption capacity obtained for Pb(II) was equal to 1.44 µmol/g. The value of lead uptake was significantly higher in comparison to the one reported for other sorbents and biosorbents. Immobilized chlorophyll a is responsible for a chelation process with stoichiometry 1:1 owing to the porphyrin rings, which was confirmed by the quantitative analysis performed by reversed-phase high-performance liquid chromatography with diode array detection. The Toth adsorption isotherm model was applicable to the description of the adsorption process of either chlorophyll a or Pb(II). The structural analysis of sorbent was done using Fourier-transform Raman spectroscopy and scanning electron microscopy with an energy dispersive X-ray detector.

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the ß-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors.

Histamine Content in Selected Production Stages of Fish Products.

Introduction: Histamine intoxication, known as scombroid fish poisoning, is caused by the consumption of foods with high levels of histamine. This biogenic amine is formed as a result of histidine decarboxylation by bacterial decarboxylases present in food, including fish and fish products. The aim of this study was to investigate the content of histamine at different production stages of canned, marinated and smoked fish. Material and Methods: Raw fish, semi-finished fish products, and the final products of the same production batches were collected between 2019 and 2022 from different fish production facilities in Poland. A total of 133 raw fish samples and 76 smoked fish, 54 brined fish, 39 canned fish and 18 marinated fish final products were analysed using high performance liquid chromatography with a diode array detector. Results: Histamine was identified in 55 (17.2%) out of 320 tested samples, including 8 samples of raw fish with a histamine level above 100 mg/kg. However, no samples of fish products had histamine content above the European Union Commission limit. Conclusion: The obtained results show that fish products on the Polish market are generally safe for consumers in regard to histamine intoxication risk.

Occurrence of Marine Biotoxins in Bivalve Molluscs Available in Poland in 2014-2018.

INTRODUCTION: Marine biotoxins are toxic substances that may cause illness and death in marine organisms and humans. This article disseminates the results of a 4-year study on the occurrence of marine biotoxins in raw bivalve molluscs purchased from Polish suppliers. MATERIAL AND METHODS: A total of 256 samples of 8 different molluscs species were analysed for the presence of biotoxins using the ELISA method for paralytic shellfish poison, diarrhoetic shellfish poison, and amnaesic shellfish poison. RESULTS: The permitted limits of marine biotoxin content were not exceeded in any of the analysed samples and the majority of them were free from these compounds. CONCLUSION: The results of the study indicate that the tested raw bivalve molluscs available in Poland were safe for consumers.

Histamine Contents in Raw Long-ripening Meat Products Commercially Available in Poland.

INTRODUCTION: Many consumers seek long-ripening meat products. The availability of these highly distinctive cured pork varieties is continuously expanding and their safety should be subject to monitoring. One of potentially harmful substances in these products is histamine. The presence of this toxic amine is reported in many countries, even in high concentrations. However, the EU has not regulated the permissible histamine content in meat, in a situation at odds with that of regulated fish and fish products. This study established the usefulness of biogenic amine testing in long-ripening pork and furnished indicative concentrations potential useful as a background for future research in preparation for EU regulative intervention. MATERIAL AND METHODS: A total of 97 samples of long-ripening meat products untreated by heat were bought from various shops in the Pulawy and Lublin regions of Poland and tested for the presence of histamine using high-performance liquid chromatography with diode array. RESULTS: The histamine concentration ranged from below limit of detection to 346.64 mg/kg, where 3.47 mg/kg was the lowest in a positive sample. Histamine was detected in 48 samples (49.5%). The maximum amount of histamine was identified in dry ham and the minimum in traditional salami. CONCLUSION: The results of this study suggest that testing meat products for biogenic amines should be a very good indicator of the food safety of long-ripening meats. In half of the tested products, levels of biogenic amines potentially toxic to consumers were determined.

Marine Tetrodotoxin as a Risk for Human Health.

Tetrodotoxin (TTX) is a toxin mainly occurring naturally in contaminated puffer fish, which are a culinary delicacy in Japan. It is also detected in various marine organisms like globefish, starfish, sunfish, stars, frogs, crabs, snails, Australian blue-ringed octopuses, and bivalve molluscs. TTX is produced by marine bacteria that are consumed mainly by fish of the Tetraodontidae family and other aquatic animals. TTX poisoning through consuming marine snails has recently begun to occur over a wider geographical extent through Taiwan, China, and Europe. This neurotoxin causes food intoxication and poses an acute risk to public health. The aim of this review is to present the most recent information about TTX and its analogues with particular regard to toxicity, methods of analysis, and risk to humans of exposure.

Histamine Content in Rennet Ripening Cheeses During Storage at Different Temperatures and Times.

INTRODUCTION: In recent years, there has been a great interest in biogenic amines such histamine, as they are associated with the quality and safety of some kinds of fermented foods. The aim of this study was to evaluate the effect of temperature and storage time on the content of histamine in cheeses. MATERIAL AND METHODS: Samples of mould and hard cheeses were examined with RP-HPLC with an organic-aqueous mobile phase containing acidic buffer and chaotropic salt. The samples were stored either at 22 ± 2°C for 42 days (mould and hard cheeses) or at 4 ± 2°C for 112 days (mould cheeses) and 133 days (hard cheeses). RESULTS: The mean total histamine content in cheeses stored at 22°C was higher than the content in those stored at 4°C, with the highest concentrations found in Gorgonzola Piccante cheese (730.47 mg/kg). Histamine concentration in some types of cheeses exceeded the toxic threshold dose, indicating that after long or inadequately cool storage they may not be safe for consumers. CONCLUSION: To protect cheeses from contamination with histamine-producing bacteria and to safeguard consumers from poisoning, factors conducive to this amine's formation should be minimised during cheese processing. Suitable temperature and time during storage of cheeses are recommended to avoid the intoxication. Monitoring of this toxin in food is necessary to ensure safety of consumers.

Effective phospholipid removal from plasma samples by solid phase extraction with the use of copper (II) modified silica gel cartridges.

The new sorbent for solid phase extraction (SPE), based on silica gel modified with a copper (II), was obtained and its application for phospholipids removal from the human plasma was tested. SPE column conditioning requirements, the volume of the plasma, the composition of the elution solvent were all established. The efficacy of the removal of phospholipids was compared for different methods such as standard protein precipitation or HybridSPE Phospholipid Ultra and HybridSPE-PPT. The sample clean-up was verified by mass spectrometry (MS) and by monitoring of chromatograms in the region between 190nm and 400nm. The Fourier Transform Infrared Spectroscopy FT-IR and confocal Raman microscopy were used to evaluating the silica gel modifications and to show the structure of lipids confined in the silica pores.