To ensure food safety and to prevent unnecessary foodborne complications this study reports fast, fully automated process for histamine determination. This method is based on magnetic separation of histamine with magnetic particles and quantification by the fluorescence intensity change of MSA modified CdSe Quantum dots. Formation of Fe2O3 particles was followed by adsorption of TiO2 on their surface. Magnetism of developed probe enabled rapid histamine isolation prior to its fluorescence detection. Quantum dots (QDs) of approx. 3 nm were prepared via facile UV irradiation. The fluorescence intensity of CdSe QDs was enhanced upon mixing with magnetically separated histamine, in concentration-dependent manner, with a detection limit of 1.6 μM. The linear calibration curve ranged between 0.07 and 4.5 mM histamine with a low LOD and LOQ of 1.6 μM and 6 μM. The detection efficiency of the method was confirmed by ion exchange chromatography. Moreover, the specificity of the sensor was evaluated and no cross-reactivity from nontarget analytes was observed. This method was successfully applied for the direct analysis of histamine in white wine providing detection limit much lower than the histamine maximum levels established by EU regulation in food samples. The recovery rate was excellent, ranging from 84 to 100% with an RSD of less than 4.0%. The main advantage of the proposed method is full automation of the analytical procedure that reduces the time and cost of the analysis, solvent consumption and sample manipulation, enabling routine analysis of large numbers of samples for histamine and highly accurate and precise results.

Central European Institute of Technology Brno University of Technology Purkynova 123 CZ 612 00 Brno Czech Republic

Department of Chemistry and Biochemistry Faculty of AgriSciences Mendel University in Brno Zemedelska 1 CZ 613 00 Brno Czech Republic

Department of Chemistry Faculty of Natural Sciences University of Tirana Blv Zog 1 No 2 1 1001 Tirana Albania

Department of Chemistry University of Agriculture in Cracow Balicka Street 122 PL 30 149 Cracow Poland

Department of Inorganic Chemistry Faculty of Science Palacky University 17 Listopadu 12 CZ 771 46 Olomouc Czech Republic

Faculty of Electrical Engineering and Communication Department of Microelectronics Brno University of Technology Technicka 3058 10 CZ 616 00 Brno Czech Republic

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$a Gagic, Milica $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Fully automated process for histamine detection based on magnetic separation and fluorescence detection / $c M. Gagic, L. Nejdl, K. Xhaxhiu, N. Cernei, O. Zitka, E. Jamroz, P. Svec, L. Richtera, P. Kopel, V. Milosavljevic, V. Adam,

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$a To ensure food safety and to prevent unnecessary foodborne complications this study reports fast, fully automated process for histamine determination. This method is based on magnetic separation of histamine with magnetic particles and quantification by the fluorescence intensity change of MSA modified CdSe Quantum dots. Formation of Fe2O3 particles was followed by adsorption of TiO2 on their surface. Magnetism of developed probe enabled rapid histamine isolation prior to its fluorescence detection. Quantum dots (QDs) of approx. 3 nm were prepared via facile UV irradiation. The fluorescence intensity of CdSe QDs was enhanced upon mixing with magnetically separated histamine, in concentration-dependent manner, with a detection limit of 1.6 μM. The linear calibration curve ranged between 0.07 and 4.5 mM histamine with a low LOD and LOQ of 1.6 μM and 6 μM. The detection efficiency of the method was confirmed by ion exchange chromatography. Moreover, the specificity of the sensor was evaluated and no cross-reactivity from nontarget analytes was observed. This method was successfully applied for the direct analysis of histamine in white wine providing detection limit much lower than the histamine maximum levels established by EU regulation in food samples. The recovery rate was excellent, ranging from 84 to 100% with an RSD of less than 4.0%. The main advantage of the proposed method is full automation of the analytical procedure that reduces the time and cost of the analysis, solvent consumption and sample manipulation, enabling routine analysis of large numbers of samples for histamine and highly accurate and precise results.

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$a Nejdl, Lukas $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Xhaxhiu, Kledi $u Department of Chemistry, Faculty of Natural Sciences, University of Tirana, Blv. Zog. I No. 2/1, 1001, Tirana, Albania.

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$a Cernei, Natalia $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Zitka, Ondrej $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Jamroz, Ewelina $u Department of Chemistry, University of Agriculture in Cracow, Balicka Street 122, PL-30-149, Cracow, Poland.

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$a Svec, Pavel $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic.

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$a Richtera, Lukas $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Kopel, Pavel $u Department of Inorganic Chemistry, Faculty of Science, Palacky University, 17. Listopadu 12, CZ-771 46, Olomouc, Czech Republic; Faculty of Electrical Engineering and Communication, Department of Microelectronics, Brno University of Technology, Technicka 3058/10, CZ-616 00, Brno, Czech Republic.

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$a Milosavljevic, Vedran $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic.

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$a Adam, Vojtech $u Department of Chemistry and Biochemistry, Faculty of AgriSciences, Mendel University in Brno, Zemedelska 1, CZ-613 00, Brno, Czech Republic; Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00, Brno, Czech Republic. Electronic address: vojtech.adam@mendelu.cz.

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