Biogenic amines (BA) are chemical compounds formed in foods that contain protein, allowing the foods to undergo a bacterial degradation process. Biogenic amines are labeled as toxic food because its consumption exceeding the FDA regulation (50 mg/kg) can be harmful to humans. Some countries also have regulations that prohibit the consumption of biogenic amines in high concentrations, especially histamine. The chromatography methods generally applied by researchers are liquid chromatography (LC) and gas chromatography (GC), where the use of a derivatization reagent is necessary to increase their sensitivity. This review is based on past and present studies about biogenic amine detection related to food samples. The rationale of this study is also to provide data on the comparison of the analytical approaches between LC and GC methods. Furthermore, the various approaches of biogenic amine determination and the most applied analytical methods have been reviewed.

Histamine is a heterocyclic amine shaped by decarboxylation of the histidine. It is a compound that lack chromophore and involatile. However, the detection of histamine is imperative due to the characteristic of histamine has given several disadvantages in food industry. This paper describes methods for histamine detection by employing high performance liquid chromatography and gas chromatography. The derivatization techniques required for both methods in order to increase the sensitivity of chromatography analysis. Two derivatizing agents were applied in this study such as 9-flourenilmethyl chloroformate (FMOC – Cl) for HPLC analysis whereas for GC analysis a N,O-bis (trimethylsilyl)acetamide (BSA) was used. Method validation was in accordance to Commission Decision 657/2002/CE. The validation of specificity, linearity, precision, accuracy, detection limit and quantitation limit results indicate that the methods were acceptable. The linear range for both methods were at 0.16 – 5.00 µg∙mL-1. The determination of histamine using GC showed the superiority of this instrument compared to HPLC. Method applicability was also checked on real sample namely mackerel in order to acquire a satisfactory recovery for both methods.

Polyurethane (PU) is a unique polymer that has versatile processing methods and mechanical properties upon the inclusion of selected additives. In this study, a freestanding bio-based polyurethane film the screen-printed electrode (SPE) was prepared by the solution casting technique, using acetone as solvent. It was a one-pot synthesis between major reactants, namely, palm kernel oil-based polyol and 4,4-methylene diisocyanate. The PU has strong adhesion on the SPE surface. The synthesized bio-based polyurethane was characterized using thermogravimetry analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy (FTIR), surface area analysis by field emission scanning electron microscope, and cyclic voltammetry. Cyclic voltammetry was employed to study electrocatalytic properties of SPE-polyurethane towards oxidation of PU. Remarkably, SPE-PU exhibited improved anodic peak current as compared to SPE itself using the differential pulse voltammetry method. Furthermore, the formation of urethane linkages (-NHC(O) backbone) after polymerization was analyzed using FTIR and confirmed by the absence of peak at 2241 cm-1 attributed to the sp-hydridized carbons atoms of C≡C bonds. The glass transition temperature of the polyurethane was detected at 78.1°C.

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Histamine is commonly present in food containing proteins, like in mackerel. Consuming fish is imperative for the improvement of human muscles. Nevertheless, some studies reported ingesting fish containing histamine more than 50 mg·kg-1 can cause toxicity. This study analyzed and determined the composition of histamine in mackerel and its products commonly consumed in Malaysia, especially on the East Coast of Malaysia. These included processed mackerel such as canned products, satay (skewed fish) and keropok lekor (fish cake/ cracker). Histamine analysis was performed using High Performance Liquid Chromatography (HPLC) equipped with a fluorescence detector. A derivatizing reaction was applied to increase the sensitivity of HPLC to histamine using 9-flourenilmethylchloroformate (FMOC-Cl). The chromatographic separation was achieved in 15 min. Method validation was in accordance to Commission Decision 657/2002/CE. The linear range was at 0.16 – 5.00 µg·mL-1 (histamine) with the LOD at 0.10 µg·mL-1 and LOQ at 0.30 µg·mL-1 . Method applicability was checked on seven real samples involving raw, cooked, and dry products, yielding acceptable recovery.

Histamine is an important substance that can be applied as a parameter for allergic reactions and food freshness. This study develops a method to produce a histamine sensor based on electrodes modified using polyurethane-LiClO4. A sensor method was developed where this sensor was produced from polyurethane. The application of 4,4′-diphenylmethane diisocyanate (hard compound) and palm kernel oil-based monoester polyol (soft compound) to produce polyurethane (PU) based on bio-polyol. The addition of lithium perchlorate (LiClO4) was done in order to increase the conductivity of PU. The oxidation process was detected using cyclic voltammetry, whereas the electrochemical impedance spectroscopy was used to analyze the conductivity of the polymer. The polyurethane-LiClO4 was attached on a screen-printed electrode (SPE) within 45 min. Moreover, the 1% LiClO4-PU-SPE presented satisfactory selectivity for the detection of histamine in the pH 7.5 solution. The LiClO4-PU-SPE presented a good correlation coefficient (R = 0.9991) in the range 0.015–1 mmol·L–1. The detection limit was 0.17 mmol·L–1. Moreover, the histamine concentration of mackerel samples was detected by the PU-SEP-LiClO4. Several amine compounds were chosen to study the selectivity of histamine detection using SPE-PU-LiClO4. The interference was from several major interfering compounds such as aniline, cadaverine, hexamine, putrescine, and xanthine. The technique showed a satisfactory selective analysis compared to the other amines. A satisfactory recovery performance toward varying concentrations of histamine was obtained at 94 and 103% for histamine at 0.01 and 0.1 mmol·L–1, respectively. The application of PU-SEP-LiClO4 as an electrochemical sensor has a great prospect to analyze histamine content in fish mackerel as a consequence of PU-SEP-LiClO4 having good selectivity and simplicity.

Biogenic amines generally can be found in fish due to amines in fish undergoing a degradation process. According to the United States Food and Drug Administration (FDA), biogenic amines in fish and fish products can cause harm to consumers if consumed more than 50 µg/mL. Thus, it is important to analyze them. Five biogenic amines such as heptylamine, histamine, tyramine, cadaverine and spermidine were extracted using soaking method with methanol 50% (v/v), afterward they were detected in fish and fish products using gas chromatography – flame ionisation detector (GC-FID) and the biogenic amines structures were confirmed using mass spectrometry (MS). The detection limits (DLs) were range at 1.20 – 2.90 µg/mL. Histamine was detected in fish and fish products such as sardine (Sardinella gibosa) and mackerel (Scomberomorus guttatus) at concentration of 5.96 and 2.69 µg/mL, respectively, whereas cadaverine was found in sardine (Sardinella gibosa) at concentration of 4.96 µg/mL. Histamine concentrations in this study were detected below 50 µg/mL which is below the permissible threshold associated with scombroid poisoing.

Determination of five biogenic amines (heptylamine, histamine, tyramine, cadaverine and spermidine) in fish was optimised and validated using gas chromatography – flame ionisation detector (GC-FID) followed by confirmation using mass spectrometry (MS). The biogenic amines were derivatised using BSA (N, O-bis (trimethylsilyl) acetamide) + TMCS (trimethylchlorosilane) as a derivatisation agent. The linear working range was between 0.9995 – 0.9999. The limit of detection (LODs) were in the range of 1.20 – 2.90 μg/mL. The efficiency of recovery for every biogenic amines, which ranged between 98.41 – 116.39%, indicated that analytical procedure can be used to extract biogenic amines in fish. Using GC-FID, the concentration of five biogenic amines were simultaneously determined in fresh and salted fish samples such as mackerel (Scomberomorus guttatus), sardine (Sardinella gibbosa), whiptail (Himantura walga), gourami (Trichogaster pectoralis) and toli shad (Tenualosa toli). Histamine is found in fresh mackerel (S. guttatus) and sardine (S. gibbosa) at concentration of 5.96 and 2.69 mg/kg, respectively. Salted sardine (S. gibbosa) has histamine concentration of 8.95 mg/kg. All histamine concentrations detected were below 50 mg/kg (FDA regulation) which is below the permissible threshold associated with scombroid poisoning. Cadaverine was detected in fresh sardine (S. gibbosa), whiptail stingray (H. walga) and salted gourami (T. pectoralis) with concentration of 4.96, 146.39 and 18.80 mg/kg, respectively. None of them has biogenic amines, and histamine within FDA regulation levels (below 50 mg/kg).