A rapid and green analytical method based on capillary electrophoresis with capacitively coupled contactless conductivity detection (C⁴D) for the determination of eight environmental pollutants, the biogenic amines (putrescine, cadaverine, spermidine, spermine, tyramine, 2-phenylamine, histamine and tryptamine), is described. The separation was achieved under normal polarity mode at 24 °C and 25 kV with a hydrodynamic injection (50 mbar for 5 s) and using a bare fused-silica capillary (95 cm length × 50 µm i.d.) (detection length of 10.5 cm from the outlet end of the capillary). The optimized background electrolyte consisted of 400 mM malic acid. C⁴D parameters were set at a fixed amplitude (50 V) and frequency (600 kHz). Under the optimum conditions, the method exhibited good linearity over the range of 1.0⁻100 µg mL−1 (R² ≥ 0.981). The limits of detection based on signal to noise (S/N) ratios of 3 and 10 were ≤0.029 µg mL−1. The method was used for the determination of seawater samples that were spiked with biogenic amines. Good recoveries (77⁻93%) were found.
Three sorbent materials (A18C6-MS, DA18C6-MS and AB18C6-MS) based on the crown ether ligands, 1-aza-18-crown-6, 1,4,10,13-tetraoxa-7,16-diazacyclo octadecane and 4'-aminobenzo-18-crown-6, respectively, were prepared by the chemical immobilization of the ligand onto mesoporous silica support. The sorbents were characterized by FT-IR, scanning electron microscopy-energy dispersive X-ray microanalysis, elemental analysis and nitrogen adsorption-desorption test. The applicability of the sorbents for the extraction of biogenic amines by the batch sorption method was extensively studied and evaluated as a function of pH, biogenic amines concentration, contact time and reusability. Under the optimized conditions, all the sorbents exhibited highest selectivity toward spermidine (SPD) compared to other biogenic amines (tryptamine, putrescine, histamine and tyramine). Among the sorbents, AB18C6-MS offer the highest capacity and best selectivity towards SPD in the presence of other biogenic amines. The AB18C6-MS sorbent can be repeatedly used three times as there was no significant degradation in the extraction of the biogenic amines (%E>85). The optimized procedure was successfully applied for the separation of SPD in food samples prior to the reversed-phase high performance liquid chromatography separation.
The intake of heterocyclic amines is influenced by the amount and type of meat and fish ingested, frequency of consumption, cooking methods, cooking temperature, and duration of cooking. In this study, the dietary intake of heterocyclic amines in Malaysia and their main sources were investigated. Forty-two samples of meat and fish were analysed by high-performance liquid chromatography with photodiode array detector to determine the concentration of the six predominant heterocyclic amines, namely: 2-amino-3-methylimidazo[4,5-f] quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f] quinoline(MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f] quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5-f] quinoxaline (7,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary intake data were obtained using a food-frequency questionnaire when interviewing 600 Malaysian respondents. The level of total heterocyclic amines in food samples studies ranged from not detected to 38.7 ng g(-1). The average daily intake level of heterocyclic amine was 553.7 ng per capita day(-1). The intake of PhIP was the highest, followed by MeIQx and MeIQ. The results reveal that fried and grilled chicken were the major dietary source of heterocyclic amines in Malaysia. However, the heterocyclic amine intake by the Malaysian population was lower than those reported from other regions.