Abstract

Food deterioration caused by microbial agents often involve the formation of biogenic amines (BAs), which can have harmful effects on human health. In this study a set of BAs - tryptamine, cadaverine, putrescine, spermine, histamine, tyramine, and spermidine, were simultaneously analysed to monitor their occurrence in different types of tuna samples. An improved extraction approach involving ultrasound-assisted microextraction (USAμET) followed by derivatization with dansyl chloride (DnsCl) and analysis by ultrahigh performance liquid chromatography (UHPLC) with fluorescence detection was validated for BAs quantification. The performance of the USAμET/UHPLC-FLD was assessed by studying the limits of detection (LOD) and quantification (LOQ), linear dynamic range (LDR), precision (intra and inter-day) and matrix effect (ME). Good linearity (r2 > 0.98), LODs (from 0.98 to 8.57 mg kg−1) and LOQs (3.20–25.6 mg kg−1) were achieved for all BAs analysed. Recoveries ranged from 76% to 106%, with relative standard deviations (RSD) lower than 5.0%. ME was determined from 7.52 to 50% and the intra and inter-day precisions ranged from 4.7 to 11.6% and 5.5–14.2%, respectively. BAs levels varied significantly from 4.09 ± 0.8 mg kg−1 of putrescine in olive oil canned samples to 577.9 ± 5.9 mg kg−1 of cadaverine in natural canned samples. Tryptamine and tyramine were not detected in any of the samples analysed, while spermine and spermidine were found in 85.7% of the assayed tuna samples. Cadaverine was the most dominant BA with concentrations ranging from 54.3 ± 2.5 mg kg−1, in olive oil canned tuna, to 577.9 ± 5.9 mg kg−1, in natural canned samples, whereas putrescine had the lowest concentration (average 6.9 ± 2.5 mg kg−1). The validated methodology revealed important improvements in terms of simplification of the experimental layout, expressed in the low sample and reagent amounts, in addition to less time-consuming and labour-intensive requirements that did not compromise the analytical performance.

Highlights

  • Fish is a food with high nutritional value and easy to digest, making it essential in human diet

  • dansyl chloride (DnsCl) was select as the derivatization reagent since allows the deriva­ tization of primary, secondary, and tertiary amines

  • Upon a literature survey of chromatographic methods for the analysis of dansylated biogenic amines (BAs), we observed a lack of optimization of the derivatization reaction at several levels, in what concerns to the sample amount and reaction conditions (DnsCl concentration, reaction time and tempera­ ture; see Table 1)

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Summary

Introduction

Fish is a food with high nutritional value and easy to digest, making it essential in human diet It is highly perishable, and its quality can drop very quickly soon after its capture, when improper handling and poor hygiene conditions are used. In such cases, the appearance of undesirable odours and flavours as a result of enzy­ matic and bacterial reactions may involve the formation of harmful compounds, as biogenic amines (BAs) (Mercogliano & Santonicola, 2019). It acts synergistically with other amines for fish poisoning and decomposition (Mercogliano & Santonicola, 2019)

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