Food Anal. Methods (2016) 9:2701–2710 DOI 10.1007/s12161-016-0452-3
SWCNT-modified carbon paste electrode as an electrochemical sensor for histamine determination in alcoholic beverages Zorica S. Stojanović 1 & Eda Mehmeti 2 & Kurt Kalcher 2 & Valéria Guzsvány 3 & Dalibor M. Stanković 4
Received: 10 November 2015 / Accepted: 16 February 2016 / Published online: 1 March 2016 # Springer Science+Business Media New York 2016
Abstract In this work, a simple and rapid electrochemical method is presented for the voltammetric determination of histamine based on carbon paste electrodes bulk-modified with single-walled carbon nanotubes. As monitored in cyclic voltammetry histamine undergoes an irreversible electrochemical oxidation with a peak potential of ca. +1.25 V (vs. Ag/AgCl, 3 mol L −1 KCl) in phosphate buffer solution (PBS, 0.1 mol L −1 , pH 6.0). At optimized differential pulse voltammetric parameters, the current response of histamine was linearly proportional to its concentration in the range from 4.5 to 720 μmol L−1. A low limit of detection of 1.26 μmol L−1 and a limit of quantification of 3.78 μmol L−1 of histamine, as well as good reproducibility (RSD = 0.48–3.40 %) were obtained using the carbon paste electrode modified with singlewalled carbon nanotubes. The proposed sensor was successfully applied to the determination of histamine in commercial beer and wine samples.
* Zorica S. Stojanović
[email protected];
[email protected]
1
Department of Applied and Engineering Chemistry, Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia
2
Institute of Chemistry - Analytical Chemistry, Karl-Franzens University Graz, A-8010, Graz, Austria
3
Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg D. Obradovića 3, 21000 Novi Sad, Serbia
4
Department of Analytical Chemistry, Innovation Center of the Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade 11000, Serbia
Keywords Histamine . Modified carbon paste electrode . Single-walled carbon nanotubes . DPV . Beer and wine samples
Introduction Histamine (β-imidazolylethylamine, HIS) is a heterocyclic primary amine and belongs to a group of compounds known as biogenic amines. In the human body, it is an important mediator involved in various physiological and pathological processes, including neurotransmission and numerous brain functions, secretion of some hormones, regulation of gastrointestinal and circulatory functions, and inflammatory reactions (Jutel et al. 2002). Besides its presence in the human body at low levels, histamine can be present as normal constituent in a variety of foods and beverages. High concentrations of histamine are found mainly in protein rich and fermented foods, such as fish, cheese, sauerkraut, beer, wine, and processed meat (Maintz and Novak 2007). In food, histamine is mainly formed by decarboxylation of the free amino acid histidine, either catalyzed by endogenous decarboxylases or by uncontrolled microbial activity during deterioration and spoilage of the foodstuff (Fernandes et al. 2001). Low levels of histamine in food are not considered as a serious health risk, but administration of elevated amounts of the amine can cause an allergy-like syndrome called histamine intolerance (Maintz and Novak 2007). The intake of food containing very high concentration of histamine results in histamine poisoning (Taylor 1986; Lehane and Olley 2000). The symptoms of such toxication relate to effects on blood vessels and smooth muscles, and include headache, nasal secretion, bronchospasm, tachycardia, extrasystoles, hypotension, edema (eyelids), and urticaria (Rauscher-Gabernig et al. 2009). The severity of the symptoms can vary considerably with the amount of
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histamine ingested and the individual’s sensitivity to histamine (Russell and Maretić 1986). Due to the potential hazardous effects to humans, the determination of histamine in food and beverages is of great importance. Additionally, histamine levels can be used as a useful indicator of freshness and quality of the food and beverages. In this content numerous methods for the determination of histamine have been reported in the literature, including thin-layer chromatography (Lieber and Taylor 1978; Tao et al. 2011), gas chromatography (Antoine et al. 2002; Hwang et al. 2003), capillary zone electrophoresis (Zhang and Sun 2004), and high-performance liquid chromatography (Bauza et al. 1995; Jensen and Marley 1995; Önal 2007; Proestos et al. 2008) as well as fluorimetric (AOAC 2002) and colorimetric assays (Patange et al. 2005). These methods are reliable and very selective but usually expensive with a slow sample throughput; they require often extensive sample cleanup and derivatization procedures in combination with qualified personnel being able to perform that analysis. Promising alternatives in this regard are electroanalytical techniques, which offer advantages such as simplicity, precision, low cost of analysis and instrumentation, possibility of miniaturization, and short analysis time. Additionally, the modification of the electrode surfaces open possibility for more sensitive and selective determination of various biologically important compounds due to the increased electron transfer rate at the electrode surface (Kalcher 1990; Karimi-Maleh et al. 2013, 2014, 2015; Najafi et al. 2014). Several works were reported on the electrochemical determination of histamine. Different types of electrochemical biosensors with immobilized amine oxidases and dehydrogenases were described (Bao et al. 2002; Keow et al. 2007; Male et al. 1996; Niculescu et al. 2000; Yamamoto et al. 2001; Zeng et al. 2000). Sarada et al. (2000) published a concise report dealing with cyclic voltammetry and flow injection analysis with glassy carbon and boron-doped diamond electrodes for the characterization of the electrochemical behavior of histamine. Some studies dealing with histamine determination are based on chronopotentiometry with a nickel-film glassy carbon electrode (Švarc-Gajić and Stojanović 2010), with a solid gold electrode (Stojanović and Švarc-Gajić 2011) and with a thin film mercury electrode (Švarc-Gajić and Stojanović 2011). Square-wave stripping voltammetric method with hanging mercury drop electrode was used for histamine determination in various fish samples (Yilmaz and Inan 2015). In order to increase the sensitivity toward histamine, some chemically modified electrodes were developed such as glassy carbon electrodes modified with lignin or with a conducting polymer coated with multi-walled carbon nanotubes (Degefu et al. 2014; Geto et al. 2014). To the best of our knowledge, no study has been reported for the determination of histamine using carbon paste electrodes modified by singlewalled carbon nanotubes.
Food Anal. Methods (2016) 9:2701–2710
Carbon nanotubes (CNTs) belong to a group of rather new nano-sized materials, and they are the subject of intensive research due to their ability to functionalize the electrode surface for various applications. There are two types of nanotubes: single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs). The structure of carbon nanotubes provides them unique electrical, physical, and chemical properties. When applied alone or as an additional constituent in fabrication of carbon paste electrode, carbon nanotubes play role of an electrocatalytic agent facilitating the electron transfer between electrode surface and electroactive species (Švancara et al. 2012). Hence, carbon nanotubes paste electrodes (CNTPEs) or carbon nanotubes-modified carbon paste electrodes, (CNT-CPEs) are now widely used in electroanalytical chemistry (Antiochia et al. 2004; Libo et al. 2007; Rivas et al. 2007; Saleh Ahammad et al. 2009; Trojanowicz 2006; Valentini et al. 2003; Wang et al. 2002; Wang 2005). In this work, a single-walled carbon nanotube-modified carbon paste electrode (SWCNT-CPE) was used for the electrochemical determination of histamine. The electrochemical behavior of histamine on SWCNT-CPE was carefully investigated and a sensitive voltammetric method was elaborated by using differential pulse mode. Practical applicability of the proposed method was tested in the determination of histamine in wine and beer samples.
Experimental Chemicals All chemicals used were of analytical grade. Histamine was supplied from Sigma Aldrich (USA). Stock solutions of free base of histamine (18 mmol L−1) were prepared weakly and stored in the dark at 4 °C. Lower concentrations were prepared freshly each day before use by appropriate dilution with supporting electrolyte. Single-walled carbon nanotubes (SWCNTs, diameter 0.7–0.9 nm, with ≥93 % carbon as SW nanotubes) and graphite powder (
