Nanomaghemite core functionalized with ion-exchange resins for isolation of biogennic amines

Biogenic amines (BAs) are basic nitrogenous low mass compounds with aliphatic (spermine, spermidine, putrescine, cadaverine), heterocyclic (e.g. tryptamine, histamine) or aromatic (e.g. tyramine) structure derived mainly from the decarboxylation of amino acids ¹. They may be formed by the action of yeast, lactic acid bacteria or other microorganisms during alcoholic and malolactic fermentation ².

Most of BAs have strong physiological effects and play important biological role as source of nitrogen and precursors for synthesis of broad spectrum of biomolecules, such as hormones or nucleic acids ³. On the other hand BAs have been widely studied as potentially toxic substances, since excessive intake of BAs manifests as food poisoning ⁴. Moreover, BAs are potential precursors for the formation of carcinogenic N-nitroso compounds ⁵.

In order to determine the concentrations of biogenic amines in biological matrices, techniques providing high resolution and sensitivity are demanded. To determine BAs is challenging because of strong polarity and no natural UV absorption nor fluorescence. Thus BAs must be pre or post-column derivatized before detection ⁶. Magnetic separation may be employed for isolation of a sample from complicated biological matrixes (food, body fluids) and may thus form the first separation and pre-concetration step prior to analysis to enhance an applied methodological approach ⁷.

The main aim of the present study is synthesis of nanomaghemite core and its functionalization with ion-exchange resins (Dowex and sulfoxyethyl cellulose), which can provide binding sites for chosen BAs (Tyramine-Tyr; Putrescine-Put; Histamine-His; Cadaverine-Cad, Spermine-Spm and Spermidine-Spd respectively). Synthetic particles were finally employed for isolation and subsequent analysis by using ion-exchange chromatography.

Figure 1: Chromatogram of mixture of six biogenic amines (His, Tyr, Put, Cad, Spm, Spd) in final concentration of 100 µg.mL-1, obtained by using ion-exchange liquid chromatography with Vis detection in wavelength of 570 nm.

Figure 2: The chromatogramms of biogenic amines (100 µg.mL-1) corresponding to (A) spermine isolated by using MAN21, (B) tyramine isolated by using MAN21, (C) putrescine isolated by using MAN21, (D) spermidine isolated by using MAN1, (E) histamine isolated by using MAN21 and (F) cadaverine isolated by using MAN21, with expression of their retention times. All records were obtained by using ion-exchange liquid chromatography with Vis detector (440 nm).

Figure 3: Expression of binding recovery of all of six biogenic amines (His, Tyr, Put, Cad, Spm, Spd) after isolation on paramagnetic particles (A) MAN21 and (B) MAN1. Biogenic amines (100 µg.mL-1) were isolated following optimized conditions and recovery was calculated from quantification of biogenic amines carried out on ion-exchange liquid chromatography.

1. Mayer, H.K.; Fiechter, G.; Fischer, E., A new ultra-pressure liquid chromatography method for the determination of biogenic amines in cheese. Journal of Chromatography A 2010, 1217, 3251-3257.
2. Lonvaud-Funel, A., Biogenic amines in wines: role of lactic acid bacteria. Fems Microbiology Letters 2001, 199, 9-13.
3. Gosetti, F.; Mazzucco, E.; Gennaro, M.C.; Marengo, E., Simultaneous determination of sixteen underivatized biogenic amines in human urine by HPLC-MS/MS. Analytical and Bioanalytical Chemistry 2013, 405, 907-916.
4. Kalac, P.; Krausova, P., A review of dietary polyamines: Formation, implications for growth and health and occurrence in foods. Food Chemistry 2005, 90, 219-230.
5. Catsburg, C.E.; Gago-Dominguez, M.; Yuan, J.M.; Castelao, J.E.; Cortessis, V.K.; Pike, M.C.; Stern, M.C., Dietary sources of N-nitroso compounds and bladder cancer risk: Findings from the Los Angeles bladder cancer study. International Journal of Cancer 2014, 134, 125-135.
6. Onal, A., A review: Current analytical methods for the determination of biogenic amines in foods. Food Chemistry 2007, 103, 1475-1486.
7. Fredericci, C.; de Campos, M.F.; Braga, A.P.V.; Nazarre, D.J.; Martin, R.V.; Landgraf, F.J.G.; Perigo, E.A., Nd-enriched particles prepared from NdFeB magnets: A potential separation route. Journal of Alloys and Compounds 2014, 615, 410-414.
8. Magro, M.; Sinigaglia, G.; Nodari, L.; Tucek, J.; Polakova, K.; Marusak, Z.; Cardillo, S.; Salviulo, G.; Russo, U.; Stevanato, R., et al., Charge binding of rhodamine derivative to OH- stabilized nanomaghemite: Universal nanocarrier for construction of magnetofluorescent biosensors. Acta Biomaterialia 2012, 8, 2068-2076.
9. Zitka, O.; Cernei, N.; Heger, Z.; Matousek, M.; Kopel, P.; Kynicky, J.; Masarik, M.; Kizek, R.; Adam, V., Microfluidic chip coupled with modified paramagnetic particles for sarcosine isolation in urine. Electrophoresis 2013, 34, 2639-2647.
10. Long, G.L.; Winefordner, J.D., Limit of detection. Analytical Chemistry 1983, 55, A712-A724.
11. Amghouz, Z.; Ancin-Azpilicueta, C.; Burusco, K.K.; Garcia, J.R.; Khainakov, S.A.; Luquin, A.; Nieto, R.; Garrido, J.J., Biogenic amines in wine: Individual and competitive adsorption on a modified zirconium phosphate. Microporous and Mesoporous Materials 2014, 197, 130-139.
12. Cernei, N.; Heger, Z.; Kopel, P.; Skladanka, J.; Zitka, O.; Adam, V.; Kizek, R., Isolation of Biogenic Amines Using Paramagnetic Microparticles Off-Line Coupled with Ion Exchange Liquid Chromatography. Chromatographia 2014, 77, 1451-1459.
13. Zitka, O.; Heger, Z.; Kominkova, M.; Skalickova, S.; Krizkova, S.; Adam, V.; Kizek, R., Preconcentration based on paramagnetic microparticles for the separation of sarcosine using hydrophilic interaction liquid chromatography coupled with coulometric detection. Journal of Separation Science 2014, 37, 465-475.
14. Heger, Z.; Cernei, N.; Guran, R.; Michalek, P.; Milosavljevic, V.; Kopel, P.; Zitka, O.; Kynicky, J.; Lany, P.; Adam, V., et al., gamma-Fe2O3 Magnetic Core Functionalized with Tetraethyl Orthosilicate and 3-Aminopropyl Triethoxysilane for an Isolation of H7N7 Influenza Serotype Virions. International Journal of Electrochemical Science 2014, 9, 3374-3385.
15. de Dardel, F.; Arden, T.V., Ion Exchangers. In Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA: 2000.

PDF