Rapid Detection Of Biogenic Amines In Fish Products By Ion Mobility Spectrometry And Its Combined Technique

As a rapid detection technology,ion mobility spectrometry(IMS)has the advantages of rapid detection,high sensitivity,and the ability to operate at atmospheric pressure and can be applied to the food safety analysis.Biogenic amines(BAs)are small nitrogen-containing compounds that are presented in the human body.However,overdose intake of biogenic amines can cause headache,lower blood pressure,and even cause serious kidney failure and other side reactions.Because fish meat is rich of protein,it provides the material fundamental for the production and accumulation of biogenic amines.In this paper,high performance liquid chromatography-electrospray ion mobility spectrometry technology was used for the simultaneous detection of seven biogenic amines in tuna,and to explore the changes of biogenic amines in tuna under different storage conditions;gas chromatography-ion mobility spectrometry technology was used to detect volatile compounds in grass carp,to explore the changes of volatile biogenic amines under different storage time and storage temperature conditions.In order to detect volatile biogenic amines in grass carp conveniently and rapidly,a secondary electrospray ionization ion mobility spectrometry method was developed to explore the changes of volatile biogenic amines under different storage time and storage temperature conditions and the determination of related indicators,such as sensory evaluation,hardness,TVB-N value to assess the freshness of fish.The main results are as follows:(1)A rapid and simultaneous detection method for non-volatile biogenic amines in tuna without derivatization procedure was established and evaluated using high performance liquid chromatography-electrospray ion mobility spectrometry technology.By combining the high-performance liquid chromatography and ion mobility spectrometry,each biogenic amine was fully separated in retention time and drift time two-dimensional space and demonstrate orthogonal separation.The detection limit of biogenic amines was 0.01-0.17 mg/kg,the quantification limit was0.03-0.57 mg/kg,the linear range of histamine and spermidine was 2-100 mg/kg,and the linear range of other biogenic amines was 0.5-10 mg/kg.The developed method was sensitive and accurate with minimum sample preparation and could be applied to the detection of biogenic amines in tuna during storage.The changes of biogenic amines in tuna samples after storage for 3 days at 15°C were also studied.When the tuna was stored at 15°C for 2.5 days,the histamine exceeded the limit standard,and its content had reached 57.75 mg/kg,indicating that the tuna had spoiled in three days without enough refrigeration.(2)The changes of volatile substances of grass carp at different storage temperatures(4°C,8°C)and storage times(0 days,4 days,12 days)were detected by gas chromatography-ion mobility spectrometry technology,and volatile biogenic amines putrescine showed an accumulation trend.After the principal component analysis of the volatile substances,the difference between volatile organic substances on different storage days could be clearly distinguished,and the correct discrimination rates could 100%(4°C)and 77.78%(8°C).(3)A method for detecting trimethylamine and other volatile biogenic amines(spermidine,β-phenethylamine,putrescine)using secondary electrospray ionization-ion mobility spectrometry(SESI-IMS)was developed.The process didn’t require extra dopants.The correlation coefficient(R~2)of each volatile biogenic amine was above 0.993,the limit of detection was 0.0008-0.0541 ppmv,and the limit of quantification was 0.0027-0.1802 ppmv.The changes of volatile biogenic amines in grass carp at different temperatures(4°C,8°C)and different storage times(total 12 days)were studied.Trimethylamine and putrescine were detected and showed an increasing trend.Relevant physical and chemical indicators such as TVB-N value increased from 7.23 mg/100 g to above 38.50 mg/100 g,which was consistent with the above trend.