Biogenic Amines In Food Samples Research Articles

The inter-molecular hydrogen bonds modulated reversible ACQ-AIE conversion and dual-states sensing applications of shikimic acid derived hydrogen bond dimers

Smart molecules with adjustable and reversible ACQ-AIE transformation which could be used as luminescence sensors both in solvent and solid-state are rarely reported. Planar luminophores with strong inter-molecular hydrogen bonds and a rotor might exhibit reversible ACQ-AIE conversion by modulating the inter-molecular hydrogen bonds. As a proof of concept, herein, two smart hydrogen bond dimers (Qufu-1 and Qufu-2) with reversible ACQ-AIE transformation were derived from the renewable bio-feedstock shikimic acid. Qufu-1 and Qufu-2 possessing a novel 4-oxo-3,4-dihydrobenzofuro[2,3-d]pyrimidine key structure and both exhibit crystallization induced ACQ (CIACQ) and precipitation induced AIE (PIAIE) in solid-state. Single crystal analysis indicates that the large planar configuration formed in the dimers of Qufu-1 and Qufu-2 due to the inter-molecular hydrogen bonds, which would result in the strong π-π stacking and ACQ in crystal. The AIE state could be facile realized by breaking the inter-molecular hydrogen bonds and changing the aggregation state from crystal to precipitation. Moreover, ACQ to AIE transformation could also accomplish for Qufu-1 and Qufu-2 in solution by modulating the inter-molecular hydrogen bonds with acid. In addition, three-level structures latent fingerprint identification in real environment and fluorescent sensing of hazardous biogenic amines in food samples were performed with Qufu-1.

Food Spoilage: Detection of Biogenic Amines in Food Samples by Enzyme-based Electrochemical Biosensors

Food Spoilage: Detection of Biogenic Amines in Food Samples by Enzyme-based Electrochemical Biosensors

Dithioerythritol functionalized gold nanoparticles−based fluorometric sensing of biogenic amines in food samples

Biogenic amines (BAs) provide information about the quality, freshness and toxicity of food products. Analysis of BAs in food such as meat, dairy products and fermented beverages is very important in terms of consumer health and product quality. In this study, a simple and sensitive nanoparticle-based fluorometric method has been developed in order to determine the total BA content of food samples. It is based on the measurement of fluorescence of the 1-alkylthio-2-alkyl-isoindole product formed from the reaction between OPA (o-phthalaldehyde) reagent with BA on the surface of gold nanoparticles (AuNPs) functionalized with the dithiol compound, 1,4-dithioerythritol (DTE), in alkaline medium. One thiol-S atom of DTE attached to AuNPs while the other thiol-S was free for the fluorogenic reaction among OPA, DTE and BA. The sensor was applied to aqueous standard solutions of histamine, tyramine, tryptamine, 2-phenylethylamine displaying a significant Stokes shift in their emission spectra (λex: 340 nm; λem: 434–466 nm). The precision and accuracy were found by applying the standard addition procedure to food samples with known concentration of histamine. In the DTE-AuNP/OPA assay, detection limits of biogenic amines were found between 4.20 and 27.1 nM, lower than those of most absorptimetric and fluorometric BA sensors. The sensor was selective to BAs and has been successfully applied to some food samples (canned fish and wine). This nanosensor may have potential for the determination of BAs in regard to food quality and safety.

A sensitive ratiometric fluorescent sensor based on carbon dots and CdTe quantum dots for visual detection of biogenic amines in food samples

A novel dual-emission ratiometric fluorescent sensor for biogenic amines (BAs) was prepared by simple mixing blue fluorescent carbon dots (CDs) and yellow fluorescent CdTe quantum dots (CdTe QDs). Based on different sensitive properties of pH, CdTe QDs and CDs were used as the response signal and internal reference signal, respectively. The developed ratiometric fluorescent sensor achieved quantitative analysis of eight kinds of BAs with rapid response (30 s) and low limits of detection (1.259–5.428 μM). Furthermore, color-tunable fluorescent test strips were constructed by easily assembling CDs and CdTe QDs onto filter paper. The obtained smart label showed a distinguishable fluorescent color variation from blue to green during the corruption of shrimp samples. The smart label with advantages of convenience and rapidness provided a method for visually monitoring the freshness of food samples.

Screen-Printed Electrode-Based Sensors for Food Spoilage Control: Bacteria and Biogenic Amines Detection.

Food spoilage is caused by the development of microorganisms, biogenic amines, and other harmful substances, which, when consumed, can lead to different health problems. Foodborne diseases can be avoided by assessing the safety and freshness of food along the production and supply chains. The routine methods for food analysis usually involve long analysis times and complex instrumentation and are performed in centralized laboratories. In this context, sensors based on screen-printed electrodes (SPEs) have gained increasing importance because of their advantageous characteristics, such as ease of use and portability, which allow fast analysis in point-of-need scenarios. This review provides a comprehensive overview of SPE-based sensors for the evaluation of food safety and freshness, focusing on the determination of bacteria and biogenic amines. After discussing the characteristics of SPEs as transducers, the main bacteria, and biogenic amines responsible for important and common foodborne diseases are described. Then, SPE-based sensors for the analysis of these bacteria and biogenic amines in food samples are discussed, comparing several parameters, such as limit of detection, analysis time, and sample type.

An in situ derivatization combined with magnetic ionic liquid-based fast dispersive liquid-liquid microextraction for determination of biogenic amines in food samples

A simple, rapid and sensitive method based on in situ derivatization combined with magnetic ionic liquid (MIL)-dispersive liquid-liquid microextraction (DLLME) was developed for the determination of biogenic amines (BAs). Six BAs (tryptamine, phenylethylamine, histamine, tyramine, spermidine, and spermine) were in situ derivatized with dansyl chloride (DNS-Cl), extracted by MIL-DLLME, and then chromatographed by high-performance liquid chromatography with ultraviolet detection (HPLC-UV). This MIL trihexyltetradecylphosphonium tetrachlorocobalt (II) [P6,6,6,14+]2[CoCl42-] was explored as the extraction solvent with the advantages of magnetic susceptibility, hydrophobicity and mobile phase compatibility. Furthermore, the MIL was designed to reduce hydrolysis in aqueous solvent as well as decrease absorbance when submitted to HPLC. In order to obtain optimized extraction efficiency, the MIL mass, the volume of derivatizing agent, the type and volume of disperser, the derivatizing and extraction time, and pH of sample solution were investigated. The proposed method was successfully applied for the analysis of wine and fish samples, and the recoveries of analytes achieved were in the range of 93.2–103.1% and 94.5–102.3%, respectively. The limits of detection/quantification for wine and fish samples were in the range of 1.3–3.9/4.1–9.9 μg/L and 1.2–3.8/3.9–9.6 μg/kg, respectively. Additionally, good reproducibility with relative standard deviations lower than 4.9% (n = 5) was obtained for the analysis of wine and fish samples. The in situ DNS-Cl derivatization and MIL-DLLME method was an efficient, rapid, environmental friendly microextraction approach for the determination of BAs in foodstuffs.

Laser Scribed Graphene Biosensor for Detection of Biogenic Amines in Food Samples Using Locally Sourced Materials.

In foods, high levels of biogenic amines (BA) are the result of microbial metabolism that could be affected by temperatures and storage conditions. Thus, the level of BA is commonly used as an indicator of food safety and quality. This manuscript outlines the development of laser scribed graphene electrodes, with locally sourced materials, for reagent-free food safety biosensing. To fabricate the biosensors, the graphene surface was functionalized with copper microparticles and diamine oxidase, purchased from a local supermarket; and then compared to biosensors fabricated with analytical grade materials. The amperometric biosensor exhibits good electrochemical performance, with an average histamine sensitivity of 23.3 µA/mM, a lower detection limit of 11.6 µM, and a response time of 7.3 s, showing similar performance to biosensors constructed from analytical grade materials. We demonstrated the application of the biosensor by testing total BA concentration in fish paste samples subjected to fermentation with lactic acid bacteria. Biogenic amines concentrations prior to lactic acid fermentation were below the detection limit of the biosensor, while concentration after fermentation was 19.24 ± 8.21 mg histamine/kg, confirming that the sensor was selective in a complex food matrix. The low-cost, rapid, and accurate device is a promising tool for biogenic amine estimation in food samples, particularly in situations where standard laboratory techniques are unavailable, or are cost prohibitive. This biosensor can be used for screening food samples, potentially limiting food waste, while reducing chances of foodborne outbreaks.

Electromembrane extraction of biogenic amines in food samples by a microfluidic-chip system followed by dabsyl derivatization prior to high performance liquid chromatography analysis

In the present research, an on-chip electromembrane extraction coupled with high performance liquid chromatography was developed for monitoring the trace levels of biogenic amines (BAs), including histamine, tryptamine, putrescine, cadaverine and spermidine in food samples. A porous polypropylene sheet membrane impregnated with an organic solvent was placed between the two parts of the chip device to separate the channels. Two platinum electrodes were mounted at the bottom of these channels, which were connected to a power supply, providing the electrical driving force for migration of ionized analytes from the sample solution through the porous sheet membrane into the acceptor phase.BAs were extracted from 2 mL aqueous sample solutions at neutral pH into 50 μL of acidified (HCl 90 mM) acceptor solution. Supported liquid membrane including NPOE containing 10% DEHP was used to ensure efficient extraction. Low voltage of 40 V was applied over the SLMs during extraction time. The influences of fundamental parameters affecting the transport of BAs were optimized. Under the optimized conditions, the relative standard deviations based on four replicate measurements were less than 8.0% and limit of detections were in range of 3.0–8.0 μg L−1. Finally, the method was successfully applied to determinate BAs in the food samples and satisfactory results (recovery > 95.6) were obtained.

A Direct and Sensitive Analysis Method for Biogenic Amines in Dairy Products by Capillary Electrophoresis Coupled with Contactless Conductivity Detection

A capillary electrophoresis method coupled to contactless conductivity detection was developed for the quantitative determination of biogenic amines. Complete resolution of five biogenic amines, which are mostly found in dairy products, were performed in less than 6 min. Separation electrolyte composition was selected as 500 mM α-hydroxyisobutyric acid (HIBA) at pH 2.05. The detection limits of the method for biogenic amines were found between 0.041 and 0.098 mg/L. The precisions for the corrected peak areas were calculated as between 2.35 and 4.25% RSD. The applicability of the method was demonstrated by analyzing biogenic amines in the cheese, yoghurt, and kefir samples. The method does not require any pre-concentration and derivatization steps and can be applied as a simple, rapid, and precise method for the direct determination of biogenic amines in food samples.

Novel approaches for the determination of biogenic amines in food samples

In this work, new analytical approaches for determination of biogenic amines in wines were developed. For the first time, we studied the derivatization of BAs in wines with naphthalene- 2,3-dicarboxaldehyde (NDA) and with dabsyl chloride (DBS) and analysis of derivatized BAs by HPLC coupled to fluorescence (HPLC-NDA-FL) and thermal lens spectrometry (HPLC-DBS-TLS) detectors. The sensitivity of the two methods (LODs HPLC-NDA-FL in the range 27-73 μg/L; LODs HPLC-DBS-TLS in the range 3.4-11 μg/L) was higher than that of the official method for biogenic amines in wines, OIV-MA-AS315-18 (60-77 μg/L). For its best performances, the HPLC-DBS-TLS technique was applied to the analysis of putrescine, cadaverine, histamine and tyramine in two white wine samples. Additionally, exploiting the Berthelot reaction, the TLS fast screening of biogenic amines in wines, following the release of ammonia by transglutaminase, was also proposed. This approach allowed us to determine total biogenic amount content in concentrations below 0.1 mg/L, expressed as equivalents of histamine.

Recent Advances in the Determination of Biogenic Amines in Food Samples by (U)HPLC.

The determination of biogenic amines (BAs) in food products stirs increasing interest because of the implications in toxicological and food quality issues. Apart from these aspects, in recent years, the relevance of BAs because of some organoleptic and descriptive concerns has been pointed out by several researchers. This overview aims at revising recent advances in the determination of BAs in food samples based on liquid chromatography. In particular, papers published in the past five years have been commented. Special attention has been paid to the great possibilities of ultrahigh-performance liquid chromatography and high-resolution mass spectrometry. With regard to applications, apart from the determination of BAs in a wide range of food matrices, novel lines of research focused on the characterization, classification, and authentication of food products based on chemometrics have also been discussed.

Application of ion chromatography for the determination of biogenic amines in food samples

Ion chromatography procedure for the simultaneous determination of histamine, tyramine, phenylethylamine, cadaverine and putrescine in different food samples is described. The simple procedure based on isocratic elution, 5 mM HNO3 without organic modifier as mobile phase and conductometric detection without suppression was proposed and discussed in details. The linearity of the tested procedure was between 0.5–5 and 5–100 mg/L, average recoveries for the standard solutions of amines varied between 98–100%, whereas in standard addition method between 96–99%, that indicated acceptable accuracy of the discussed method. The satisfactory reproducibility was proved by values of coefficient of variations (CV) in the range 0.2–5.0% for all tested food samples. The proposed method reveals a number of advantages: fast elution of analytes without mobile phase conductivity suppression, lack of derivatization step, simple sample preparation and environmentally friendly character.

Application of Ion Chromatography for the Determination of Biogenic Amines in Food Samples

Ion chromatography procedure for the simultaneous determination of histamine, tyramine, phe� nylethylamine, cadaverine and putrescine in different food samples is described. The simple procedure based on isocratic elution, 5 mM HNO3 without organic modifier as mobile phase and conductometric detection without suppression was proposed and discussed in details. The linearity of the tested procedure was between 0.5-5 and 5-100 mg/L, average recoveries for the standard solutions of amines varied between 98-100%, whereas in standard addition method between 96-99%, that indicated acceptable accuracy of the discussed method. The satisfactory reproducibility was proved by values of coefficient of variations (CV) in the range 0.2-5.0% for all tested food samples. The proposed method reveals a number of advantages: fast elution of analytes without mobile phase conductivity suppression, lack of derivatization step, simple sample prepara� tion and environmentally friendly character.

A review of the liquid chromatographic methods for the determination of biogenic amines in foods

Biogenic amines (BAs) are biologically active molecules which have aliphatic (putrescine, cadaverine, spermine, spermidine), aromatic (tyramine, phenylethylamine) or heterocyclic (histamine, tryptamine) structures. They can be detected in raw and processed foods which are formed and degraded through several pathways during the metabolic processes of animals, plants and microorganisms. The identification and quantitation procedures of BAs in food samples are very important, because BAs are considered as the indicators of food quality and freshness. The determination of BAs are commonly achieved by separation techniques such as high-performance liquid chromatography (HPLC), gas chromatography (GC) and capillary electrophoresis (CE). In this article, analysis of BAs in foods were reviewed from 2007 to present.

A multiresidual method based on ion-exchange chromatography with conductivity detection for the determination of biogenic amines in food and beverages

In the present work a sensitive and accurate method by ion chromatography and conductimetric detection has been developed for the determination of biogenic amines in food samples at microgram per kilogram levels. The optimized extraction procedure of trimethylamine, triethylamine, putrescine, cadaverine, histamine, agmatine, spermidine, and spermine from real samples, as well as the separation conditions based on a multilinear gradient elution with methanesulfonic acid and the use of a weak ionic exchange column, have provided excellent results in terms of resolution and separation efficiency. Extended calibration curves (up to 200 mg/kg, r > 0.9995) were obtained for all the analyzed compounds. The method gave detection limits in the range 23-65 μg/kg and quantification limits in spiked blank real samples in the range 65-198 μg/kg. Recovery values ranged from 82 to 103 %, and for all amines, a good repeatability was obtained with precision levels in the range 0.03-0.32 % (n = 4). The feasibility and potential of the method were tested by the analysis of real samples, such as tinned tuna fish, anchovies, cheese, wine, olives, and salami.

Simultaneous determination of 23 amino acids and 7 biogenic amines in fermented food samples by liquid chromatography/quadrupole time-of-flight mass spectrometry

A novel liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC-Q-TOFMS) method was developed for the simultaneous determination of 23 amino acids and 7 biogenic amines in food samples. These analytes were pre-column derivatized with dansyl chloride and then separated in an Acquity column (1.7 μm; 2.1 mm × 100 mm). The separation of 31 compounds including an internal standard was achieved within 25 min at a flow rate of 0.2 mL/min. The method linearity for each amino acid and biogenic amine had a relatively wide range with r(2)>0.99. The intra- and inter-day precision, expressed as relative standard deviation (RSD), ranged from 1.1 to 4.6% and from 2.0 to 11.2%, respectively. The limit of detection was between 0.005 and 0.4 μg/mL. With a simple dilution, recoveries of around 80-120% were obtained for most of the compounds. No significant matrix effect was observed, and the developed method was successfully applied to the analysis of amino acids and biogenic amines in beer, cheese and sausage samples.

A 4-hydroxy- N′-[( E)-(2-hydroxyphenyl)methylidene]benzohydrazide-based sorbent material for the extraction-HPLC determination of biogenic amines in food samples

A sorbent material based on a newly synthesized hydrazone ligand, 4-hydroxy- N′-[( E)-(2-hydroxyphenyl)methylidene]benzohydrazide was prepared by immobilizing the ligand into a silica sol–gel matrix. The capability of the sorbent material for the extraction of seven biogenic amines (BAs), i.e., tryptamine (TRY), β-phenylethylamine (PEA), putrescine (PUT), cadaverine (CAD), histamine (HIS), tyramine (TYR), and spermidine (SPD) was studied. Under the adopted conditions, the sorbent showed good selectivity towards PUT, CAD, HIS and SPD (% extraction (%E) > 96) while %E for TYR, TRY and PEA were 82.0, 78.9 and 46.4%, respectively. The sorbent could be used up to six extraction cycles for SPD, CAD and PUT and was applied to the determination of food samples (“budu”, ketchup, orange juice, soy sauce) that were spiked with 20 mg L −1 of the BAs. The extracted analytes were derivatized with dansyl chloride before the HPLC determination. With the exception of HIS and TYR in “budu” sample, reasonable recoveries were found for the other analytes in all the tested food samples.

Non‐ionic micellar electrokinetic chromatography with laser‐induced fluorescence: A new method tested with biogenic amines in brined and dry‐salted fish

A non-ionic micellar electrokinetic chromatography method coupled to laser-induced fluorescence detection was developed for the quantitative determination of biogenic amines. Complete resolution of six biogenic amines - FITC derivatives - was achieved in less than 10 min, employing 10 mM Brij 35 in 75 mM borate buffer and at pH 9.7 as the running electrolyte. Relative fluorescence intensities of biogenic amines enhanched considerably and separation time decreased considerably when Brij 35 was substituted for SDS in the same buffer. The detection limits of the method for biogenic amines were found between 0.416 and 1.26 nM. The precisions for the corrected peak areas were calculated as between 1.63 and 3.24 %RSD. The applicability of the method was demonstrated by analyzing biogenic amines in the processed, brined, and dry-salted fish samples. The method is simple and rapid, and widely applicable for the determination of biogenic amines in food samples.

In situ derivatization hollow fibre liquid-phase microextraction for the determination of biogenic amines in food samples

Hollow fibre liquid-phase microextraction with in situ derivatization using dansyl chloride has been successfully developed for the high-performance liquid chromatography-ultraviolet (HPLC-UV) determination of the biogenic amines (tryptamine, putrescine, cadaverine, histamine, tyramine, spermidine) in food samples. Parameters affecting the performance of the in situ derivatization process such as type of extraction solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Under the optimized conditions (extraction solvent, dihexyl ether; acceptor phase, 0.1 M HCl; extraction time, 30 min; extraction temperature, 26 °C; without addition of salt), enrichment factors varying from 47 to 456 were achieved. Good linearity of the analytes was obtained over a concentration range of 0.1–5 μg mL −1 (with correlation coefficients of 0.9901–0.9974). The limits of detection and quantification based on a signal-to-noise ratio of 3–10, ranged from 0.0075 to 0.030 μg mL −1 and 0.03 to 0.10 μg mL −1, respectively. The relative standard deviations based on the peak areas for six replicate analysis of water spiked with 0.5 μg mL −1 of each biogenic amine were lower than 7.5%. The method was successfully applied to shrimp sauce and tomato ketchup samples, offering an interesting alternative to liquid–liquid extraction and solid phase extraction for the analysis of biogenic amines in food samples.

Determination of biogenic amines in food samples using derivatization followed by liquid chromatography/mass spectrometry

A liquid chromatography (LC)/mass spectrometry method was developed for the determination of selected biogenic amines in various fish and other food samples. It is based on a precolumn derivatization of the amines with succinimidylferrocenyl propionate under formation of the respective amides and their reversed-phase liquid-chromatographic separation with subsequent electrospray ionization mass-spectrometric detection. Deuterated putescine, cadaverine, and histamine are added prior to the derivatization as internal standards that are coeluted, thus allowing excellent reproducibility of the analysis to be achieved. Depending on the analyte, the limits of detection were between 1.2 and 19.0 mg/kg, covering between 2 and 3 decades of linearity. The limit of detection and the linear range for histamine are suitable for the surveillance of the only defined European threshold for biogenic amines in fish samples. Compared with the established ortho-phthalaldehyde (OPA)/LC/fluorescence method, the newly developed method allows an unambiguous identification of the biogenic amines by their mass spectra in addition to only retention times, a fivefold acceleration of the separation, and independency from the sample matrix owing to the isotope-labeled internal standards. Various fish, calamari, and salami samples were successfully analyzed with the new method and validated with an independent OPA/LC/fluorescence method.