Detection Of Biogenic Amines Research Articles

The Importance of Derivatizing Reagent in Chromatography Applications for Biogenic Amine Detection in Food and Beverages.

Biogenic amines (BA) are chemical compounds formed in foods that contain protein, allowing the foods to undergo a bacterial degradation process. Biogenic amines are labeled as toxic food because its consumption exceeding the FDA regulation (50 mg/kg) can be harmful to humans. Some countries also have regulations that prohibit the consumption of biogenic amines in high concentrations, especially histamine. The chromatography methods generally applied by researchers are liquid chromatography (LC) and gas chromatography (GC), where the use of a derivatization reagent is necessary to increase their sensitivity. This review is based on past and present studies about biogenic amine detection related to food samples. The rationale of this study is also to provide data on the comparison of the analytical approaches between LC and GC methods. Furthermore, the various approaches of biogenic amine determination and the most applied analytical methods have been reviewed.

Detection of biogenic amines in mead of social bee

Mead is an alcoholic beverage, resulting from the fermentation of honey and water, although it is an old drink, some fermentation products are still unknown. Biogenic amines have driven research on food and beverages due to their toxicity and capacity to cause damage to the human health. This study aimed to evaluate the presence of biogenic amines in mead from honey of two species of social bees, using different fining agents (bentonite, banana peel flour, and passion fruit peel flour) and storage in oak barrel for 120 days. We observed the presence of three biogenic amines for each type of mead. Putrescine was reported only in samples of mead of Apis mellifera. Tryptamine and histamine were not detected, while tyramine was observed in the mead samples of honey from Melipona quadrifasciata anthidioides. Samples clarified with fruit peels increased the number of amines. In the analysis of the histamine, used as standard, obtained limits of detection and quantification of 2.47 mg/L and of 7.48 mg/L, respectively. In this study, the amines observed remained below the limit of detection, and did not pose a risk to consumers. The finings used demonstrated a profile similar to the control mead, and its use was satisfactory.

Simultaneous detection of biogenic amines and aminobutyric acid isomers in high-protein forages

High performance liquid chromatography (HPLC) was applied for simultaneous determination of selected biogenic amines and non-proteinogenic amino acids in fermented forage, i.e. silage. The four most frequently occurring biogenic amines in silage and three isomers of aminobutyric acid, potentially impairing welfare and health of farm animals, were separated in a single analysis. Without time-consuming extraction and concentration procedures, these compounds were analysed as N-substituted phenylthiocarbamyl derivatives using a reversed-phase C18 column. The method is suitable for rapid determination of the extent of amino acid decomposition during fermentation in forage with high protein content.

Zinc(II) salphen complex-based fluorescence optical sensor for biogenic amine detection.

Biogenic amines have attracted interest among researchers because of their importance as biomarkers in determining the quality of food freshness in the food industry. A rapid and simple technique that is able to detect biogenic amines is needed. In this work, a new optical sensing material for one of the biogenic amines, histamine, based on a new zinc(II) salphen complex was developed. The binding of zinc(II) complexes without an electron-withdrawing group (complex 1) and with electron-withdrawing groups (F, complex 2; Cl, complex 3) to histamine resulted in enhancement of fluorescence. All complexes exhibited high affinity for histamine [binding constant of (7.14 ± 0.80) × 104, (3.33 ± 0.03) × 105, and (2.35 ± 0.14) × 105 M-1, respectively]. Complex 2 was chosen as the sensing material for further development of an optical sensor for biogenic amines in the following step since it displayed enhanced optical properties in comparison with complexes 1 and 3. The optical sensor for biogenic amines used silica microparticles as the immobilisation support and histamine as the analyte. The optical sensor had a limit of detection for histamine of 4.4 × 10-12 M, with a linear working range between 1.0 × 10-11 and 1.0 × 10-6 M (R2 = 0.9844). The sensor showed good reproducibility, with a low relative standard deviation (5.5 %). In addition, the sensor exhibited good selectivity towards histamine and cadaverine over other amines, such as 1,2-phenylenediamine, triethylamine, and trimethylamine. Recovery and real sample studies suggested that complex 2 could be a promising biogenic amine optical sensing material that can be applied in the food industry, especially in controlling the safety of food for it to remain fresh and healthy for consumption.

Naphthyl End-Capped Terthiophene-Based Chemiresistive Sensors for Biogenic Amine Detection and Meat Spoilage Monitoring.

A reliable and sensitive detection of biogenic amines (BAs) is essential to ensure food safety and maintain public health. In this study, two naphthyl end-capped terthiophene derivatives, namely, 5-(naphthalen-1-yl)-2,2':5',2''-terthiophene (NA-3T) and 5,5''-di(naphthalen-1-yl)-2,2':5',2''-terthiophene (NA-3T-NA), were employed to develop chemiresistive sensors for detecting gaseous BAs. In contrast to NA-3T, the NA-3T-NA-based sensor showed a higher sensitivity for trimethylamine (TMA) with an experimental detection limit lower than 22 ppm, and for aromatic BAs, including dopamine, histamine, tryptamine, and tyramine. Additionally, the recovery time for TMA was found to be shorter than 23 s. In addition, both sensors were successfully used for an in situ evaluation of meat freshness by monitoring the concentration of relevant volatile BAs. The difference in the sensing performances of the two chemiresistive sensors was tentatively ascribed to different packing structures of the derivatives and the adlayer structures of the films developed with the compounds.

Dynamic Detection of Biogenic Amines as a Quality Indicator and Their Relationship with Free Amino Acids Profiles in Large Yellow Croaker (Pseudosciaena crocea).

The production of biogenic amines (BAs) set considerable obstacles in seafood preservation. However, the characteristic BAs and their roles in the spoilage profiles in large yellow croaker were still poorly understood. The BAs contents, free amino acids (FAAs) contents, aerobic bacterial count, sensory evaluation and several characteristic physicochemical indexes were monitored during storage at 4 °C. It's forcefully uncovered that the putrescine and cadaverine were the main BAs and the sum value of them could be used as a novel quality indicator instead of BAI. The reasonable limitation for unaccepted corruption was suggested be around 60 mg/kg. The regression model (r > 0.8, P < 0.05) at 4 °C indicated a significant correlation between the main BAs and total volatile basic nitrogen (TVB-N), protein hydrolysis index (P.I.%) as well as pH value, offering a new interpretation form for the physiochemical properties of BAs in aquatic products. Additionally, the evolution of FAAs show the predominant role of lysine, proline, histidine, glycine, and alanine during the whole storage and it can be concluded that BAs biosynthesis in large yellow croaker were moderately related with their precursor substance. This work provides a preliminary insight into the origin of BAs in large yellow croaker. PRACTICAL APPLICATION: It was proposed that the sum value of putrescine and cadaverine which were the main BAs can be used as a novel quality indicator instead of BAI in large yellow croaker. And the regression models of BAs and other physiochemical indexes provided a new perspective for comprehending the spoilage profiles involving BAs biosynthesis. The study may potentially contribute to improving the evaluation of seafood freshness and provide new target site for seafood preservation.

Indicator Layers Based on Ethylene-Vinyl Acetate Copolymer (EVA) and Dicyanovinyl Azobenzene Dyes for Fast and Selective Evaluation of Vaporous Biogenic Amines.

The article presents naked-eye methods for fast, sensitive, and selective detection of isopentylamine and cadaverine vapours based on 4-N,N-dioctylamino-4′-dicyanovinylazobenzene (CR-528) and 4-N,N-dioctylamino-2′-nitro-4′-dicyanovinylazobenzene (CR-555) dyes immobilized in ethylene-vinyl acetate copolymer (EVA). The reaction of CR-528/EVA and CR-555/EVA indicator layers with isopentylamine vapours caused a vivid colour change from pink/purple to yellow/orange-yellow. Additionally, CR-555/EVA showed colour changes upon exposure to cadaverine. The colour changes were analysed by ultraviolet–visible (UV/VIS) molecular absorption spectroscopy for amine quantification, and the method was partially validated for the detection limit, sensitivity, and linear concentration range. The lowest detection limits were reached with CR-555/EVA indicator layers (0.41 ppm for isopentylamine and 1.80 ppm for cadaverine). The indicator layers based on EVA and dicyanovinyl azobenzene dyes complement the existing library of colorimetric probes for the detection of biogenic amines and show great potential for food quality control.

Detection of biogenic amines in pet food ingredients by RP-HPLC with automated dansyl chloride derivatization.

The detection of biogenic amines is of significant interest to the food industry, as they can be used as indicators of food spoilage and they are potentially toxic. Because of their importance, there is a need for automated methods suitable for industry use that can detect a wide range of biogenic amines at sufficient levels for food analysis. In this work, optimized conditions for the automated determination of biogenic amines (histamine, putrescine, cadaverine, spermine, spermidine, tyramine, and tryptamine) derivatized with dansyl chloride are presented. Limits of detection below 0.2ppm were achieved for seven biogenic amines and percentage recoveries were between 80 and 109% for the seven analytes spiked into meat meal samples. The method is simple and compared well to an existing method for the detection of biogenic amines in pet food ingredients.

Fluorescent ternary complexes of some biogenic amines and their metabolites with europium and oxytetracycline for applications in the chemical analysis

New ternary complexes of europium with oxytetracycline possessing the intense fluorescence have been obtained for prospective applications in the high-sensitive detection of biogenic amines and their metabolites in biological fluids. Their stability constants have been determined using the Foster–Hammick–Wardley method based on the fluorescent spectroscopy data. The dependence between structure differences, stability constants of ternary complexes of europium–oxytetracycline with biogenic amines, and their metabolites, and sensitivity of their determination has been established.

Polyaniline-based cadaverine sensor through digital image colorimetry

AbstractThe detection of biogenic amines is important due to the their correlation with spoilage and toxicity. Polyaniline (PANI) is a polymer capable of changing color from blue to green andvice versathrough acid-base reactions. This study tested the potential of PANI as a sensing material for the presence of cadaverine. PANI was fabricated on nylon cloths through the redox reaction of aniline and ammonium persulfate. The PANI-coated nylon cloths were exposed to different amounts of cadaverine in a fixed reaction time of 5 min. Through digital image colorimetry, plots of the different color values vs. concentration were prepared and the curve with the highest linearity was obtained using the yellow value. Values for limit of detection (LOD) and limit of quantification (LOQ) were calculated to be 0.8816 mmand 2.9386 mm,respectively. An Android application which analyzes the color values of the PANI image in relation to the amount of cadaverine was also developed.

Rapid and ultrasensitive detection of biogenic amines with colorimetric sensor array

Biogenic amine (BA) is an appropriate indicator of food spoilage. Thus, it is important to develop simple, portable and highly sensitive amine sensors for food safety. Here, detection of biogenic amines was investigated using a colorimetric sensor array fabricated from complexes of pH-sensitive dyes and nanomaterials. The Brønsted-Lowry acid-base reaction between the complex and BAs forms different amine salts. Variation in the alkalinity of these amines causes significant and distinct color changes in the pH-sensitive dyes. Eight common BAs can be differentiated from visual observation of difference maps alone. In conjunction with pattern recognition, the sensor array clearly differentiates eight gaseous amines with ≥92.6% accuracy and allows rapid quantification of trimethylamine (TMA) vapors with an impressive limit of detection (LOD) of 1.3 ppb. It also shows excellent chemical stability against changes in temperature and humidity. This sensor array for amines can be used as an alternative and promising tool for food monitoring.

Detection of biogenic amines using a nitrated conjugated polymer

Nitrated polythiophene (NPTh) was examined for the detection of amine vapors. When the polymer film was exposed to vapors of biogenic amines (BAs) such as ethylenediamine, putrescine, and cadaverine, its color darkened instantly. Accordingly, the ultraviolet-visible (UV–vis) absorption spectra showed a significant hyperchromic shift, indicating the formation of an intermolecular charge transfer complex (NPThδ+-BAδ−) between the polymer and analyte. On the other hand, the change in absorption was relatively small for non-BA vapors. The absorption response rates of NPTh to the BAs were quite different because of the differences in their saturated vapor pressures. A linear relationship between vapor concentration (z) and absorption change (y: A/A0, where, A and A0 are the absorbances after and before exposure to the amine, respectively) was established, given by the equation z = k(y–1), where k = (concsat/teq)/a, concsat is the saturated vapor concentration, and teq is the exposure time necessary to reach an equilibrium in the absorption change. The k values for ethylenediamine, putrescine, and cadaverine were determined to be 5.01 × 103, 0.83 × 103, and 0.40 × 103 ppm, respectively. This equation can be used to determine the unknown BA vapor concentration by UV–vis spectroscopic analysis.

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.

Detection of biogenic amines and microbial safety assessment of novel Meju fermented with addition of Nelumbo nucifera, Ginkgo biloba, and Allium sativum

Meju, a cooked and fermented soy bean based food product, is used as a major ingredient in Korean traditional fermented foods such as Doenjang. We developed a novel type of Meju using single and combined extracts of Allium sativum (garlic clove), Nelumbo nucifera (lotus leaves), and Ginkgo biloba (ginkgo leaves) at 1% and 10% concentrations to improve the safety of Meju-based fermented products. Biogenic amines (BAs) in protein-rich fermented food products pose considerable toxical risks. The objective of this study was to investigate the effects of adding selected plant extracts in Meju samples during fermentation. Nine BAs, including tryptamine, 2-phenylethylamine, putrescine, cadaverine, agmatine, histamine, tyramine, spermidine and spermine, were isolated from Meju samples after sample derivatization with dansyl chloride and analyzed by high performance liquid chromatography. As a result, all tested Meju samples with added plant extracts showed total BAs levels in the range of 20.12 ± 2.03 to 118.42 ± 10.68 mg/100 g, which were below the safety limit set by various regulatory authorities (USFDA/KFDA/EFSA). However, among all tested Meju samples, LOM10 (Meju fermented with Nelumbo nucifera at 10% concentration) showed higher levels of BAs content than others either due to batch-to-batch variability or reduced beneficial microorganisms and/or due to increase in BA forming microorganisms. Also, none of the samples showed the aflatoxin level above the detection limit. Furthermore, all the tested Meju samples improved microbial safety as confirmed by the complete absence of Salmonella species and Staphylococcus aureus. However, some of the Meju samples showed the presence of coliforms (in range of 1.6 × 100–1.1 × 103 CFU/g), which is under regulatory limits. These results suggested that the use of plant extracts in Meju during fermentation have potential to improve microbial and toxicological safety of Meju products.

Sub-nanomolar detection of biogenic amines by SERS effect induced by hairy Janus silver nanoparticles

Surface enhanced Raman scattering (SERS) is largely used as a transduction method for analytes detection in liquid and vapor phase. In particular, SERS effect was promoted by a plethora of different metal and semiconducting nanoparticles (NPs) and silver and gold nanoparticles appear particularly suitable for this application. Nevertheless, silver nanoparticles intrinsic propensity to aggregate in large clusters reduces the possibility to use naked nanoparticles in SERS applications, for this reason they are usually functionalized with organic molecules. This approach inhibits the aggregation process but, on the other hand, reduces the surficial area of the NPs able to interact with the analyte molecules. In the present work, we propose a simple method to obtain surficial anisotropic Janus silver nanoparticles: octadecylamine was used to stabilize the nanoparticles and to promote the deposition of the silver nanoparticles on a solid substrate. The AgNPs/octadecylamine nanostructures showed the typical “hairy” Janus morphology and a strong SERS effect was observed when two biogenic amines, i. e. 2-phenylethylamine and tyramine, were fluxed on the solid film. SERS phenomenon was studied as a function both of the chemical structure of the fluxed amine and of the distance between the aromatic moiety and the nanoparticle allowing to propose the AgNPs/octadecylamine Janus nanoparticles as an active layer for the detection of phenylethylamine and tyramine in picomolar concentration.

Competitive fluorescent pseudo-immunoassay exploiting molecularly imprinted polymers for the detection of biogenic amines in fish matrix

We developed a competitive fluorescent molecularly imprinted polymer (MIP) assay to detect biogenic amines in fish samples. MIPs synthesized by precipitation polymerization using histamine as template were used in a batch binding assay analogous to competitive fluoroimmunoassays. Introducing a complex sample matrix, such as fish extract, into the assay changes the environment and the binding conditions, therefore the importance of the sample preparation is extensively discussed. Several extraction and purification methods for fish were comprehensively studied, and an optimal clean-up procedure for fish samples using liquid-liquid extraction was developed. The feasibility of the competitive MIP assay was shown in the purified fish extract over a broad histamine range (1 − 430µM). The MIP had the highest affinity towards histamine, but recognized also the structurally similar biogenic amines tyramine and tryptamine, as well as spermine and spermidine, providing simultaneous analysis and assessment of the total amount of biogenic amines.

Water-soluble naphthalene diimides: synthesis, optical properties, and colorimetric detection of biogenic amines

Biocompatible water-soluble naphthalene diimides (NDIs) were synthesized and a core-dichlorinated NDI was shown to detect primary amines and biogenic diamines.

An electrolyte-gated polythiophene transistor for the detection of biogenic amines in water.

We herein propose a novel sensing strategy for biogenic amines using an electrolyte-gated polythiophene transistor. This ultra-low voltage operatable device responds to amines on the basis of the molecular recognition ability of a polythiophene pendant with a carboxy side-chain, which indicates that the sensing platform can contribute to the realisation of easy-to-fabricate and integrated chemical sensors.

Functional electrospun nanofibers for multimodal sensitive detection of biogenic amines in food via a simple dipstick assay.

Electrospun nanofibers (ENFs) are promising materials for rapid diagnostic tests like lateral flow assays and dipsticks because they offer an immense surface area while excluding minimal volume, a variety of functional surface groups, and can entrap functional additives within their interior. Here, we show that ENFs on sample pads are superior in comparison to standard polymer membranes for the optical detection of biogenic amines (BAs) in food using a dipstick format. Specifically, cellulose acetate (CA) fibers doped with 2mg/mL of the chromogenic and fluorogenic amine-reactive chameleon dye Py-1 were electrospun into uniform anionic mats. Those extract cationic BAs from real samples and Py-1 transduces BA concentrations into a change of color, reflectance, and fluorescence. Dropping a BA sample onto the nanofiber mat converts the weakly fluorescent pyrylium dye Py-1 into a strongly red emitting pyridinium dye. For the first time, a simple UV lamp excites fluorescence and a digital camera acts as detector. The intensity ratio of the red to the blue channel of the digital image is dependent on the concentration of most relevant BAs indicating food spoilage from 10 to 250μM. This matches the permitted limits for BAs in foods and no false positive signals arise from secondary and tertiary amines. BA detection in seafood samples was also demonstrated successfully. The nanofiber mat dipsticks were up to sixfold more sensitive than those using a polymer membrane with the same dye embedded. Hence, nanofiber-based tests are not only superior to polymer-based dipstick assays, but will also improve the performance of established tests related to food safety, medical diagnostics, and environmental testing. Graphical Absract ᅟ.

A Highly Sensitive Bimodal Detection of Amine Vapours Based on Aggregation Induced Emission of 1,2-Dihydroquinoxaline Derivatives.

The detection of food spoilage is a major concern in food safety as large amounts of food are transported globally. Direct analysis of food samples is often time-consuming and requires expensive analytical instrumentation. A much simpler and more cost-effective method for monitoring food fermentation is to detect biogenic amines generated as a by-product during food decomposition. In this work, a series of 1,2-dihydroquinoxaline derivatives (DQs) with aggregation-induced emission (AIE) characteristics were synthesised and their protonated forms, that is, H+ DQs, can be utilised for the sensitive detection of biogenic amines. For example, upon exposure to amine vapours, deprotonation occurs that converts the red-coloured, non-emissive H+ DQ2 back to its yellow-coloured, fluorescent parent form. The bimodal absorption and emission changes endow the system with high sensitivity, capable of detecting ammonia vapour at a concentration of as low as 690 ppb. Taking advantage of this, H+ DQ2 was successfully applied for the detection of food spoilage and was established as a robust and cost effective technique to monitor food safety.