Preface

Human health can be affected by minor food compounds that sometimes are neglected by consumers. Biogenic amines (BAs) are naturally occurring amines and are a group belonging to the aforementioned compounds. Their concentrations are positively affected by microbial fermentation of food or during food spoilage. Many analytical methods are published regarding extraction and characterization of these minor food substances.

BAs are nitrogen-containing compounds formed by the decarboxylation of amino acids or by amination and transamination of ketones and aldehydes. The structure of BAs can be aliphatic, aromatic, and heterocyclic. Depending on the number of amine groups, amines are classified into monoamines (tyramine and phenylethylamine), diamines (histamine, putrescine, and cadaverine), or polyamines (spermidine and spermine). Currently, there are research papers that have classified cadaverine, putrescine, spermine, and spermidine among polyamines.

> **Proestos Charalampos** Assistant Professor in Food Chemistry, Department of Chemistry, Laboratory of Food Chemistry, National and Kapodistrian University of Athens, Athens, Greece

**1**

Section 1

Introduction

Section 1 Introduction

**3**

**Chapter 1**

*Proestos Charalampos*

**1. Introduction**

BAs may be present.

**3. Safety issues and function**

Introductory Chapter: Current

Knowledge on Biogenic Amines

Human health can be affected by minor food compounds which sometimes are neglected by consumers. Biogenic amines are naturally occurred amines and for sure they can be one group belonging to the aforementioned compounds. Their concentrations are positively affected by microbial fermentation of food or during food spoilage. Many analytical methods are published regarding extraction and characterization of these minor food substances. Biogenic amines (BAs) are nitrogen-contained compounds occurring by decarboxylation of amino acids or by amination and ransamination of ketones and aldehydes. The structure of BAs can be aliphatic, aromatic, and heterocyclic. Depending on the number of amine groups, amines are classified into monoamines (tyramine and phenylethylamine), diamines (histamine, putrescine, and cadaverine), or polyamines (spermidine and spermine). Currently, there are research papers that have classified cadaverine,

BAs are found in a variety of food products including seafood, meat, dairy, fruits, vegetables, nuts, chocolates, and fermented products. Foods containing proteins or amino acids in free form can have microbial or biochemical activity and

Fermented products can contain BAs such as milk products, for example, cheese 5–4500 ppm, wines 5–135 ppm, beer 2.7–14 ppm. BAs can also be present in foods that are spoiled or in the beginning of spoilage such as fish and fish products 2300–5000 ppm, animal liver like beef about 330 ppm, processed meat and meat products 9–650 ppm [2]. BAs can be used in nonfermented products such as decomposition markers or indicator compounds. Deteriorated foods contain high amounts of BAs with the most abundant being cadaverine and putrescine. BAs contained in high amounts can have a serious health risk for consumers who belong to sensitive population. Symptoms may include hot flushes, respiratory discomfort, nausea, cold sweat, headaches, palpitations, red rash, low or high blood pressure. Alcohol consuming and presence of acetaldehyde may increase sensitivity to biogenic amines.

Scombroid poisoning which is caused due to histamine presence is a very important issue that is why only histamine has a regulatory limit, according to EU regulation (maximum 200 mg/kg in fresh fish and 400 mg/kg in fish products

putrescine, spermine, and spermidine among polyamines [1].

**2. BAs occurrence in foods and health effect**

### **Chapter 1**

## Introductory Chapter: Current Knowledge on Biogenic Amines

*Proestos Charalampos*

### **1. Introduction**

Human health can be affected by minor food compounds which sometimes are neglected by consumers. Biogenic amines are naturally occurred amines and for sure they can be one group belonging to the aforementioned compounds. Their concentrations are positively affected by microbial fermentation of food or during food spoilage. Many analytical methods are published regarding extraction and characterization of these minor food substances. Biogenic amines (BAs) are nitrogen-contained compounds occurring by decarboxylation of amino acids or by amination and ransamination of ketones and aldehydes. The structure of BAs can be aliphatic, aromatic, and heterocyclic. Depending on the number of amine groups, amines are classified into monoamines (tyramine and phenylethylamine), diamines (histamine, putrescine, and cadaverine), or polyamines (spermidine and spermine). Currently, there are research papers that have classified cadaverine, putrescine, spermine, and spermidine among polyamines [1].

### **2. BAs occurrence in foods and health effect**

BAs are found in a variety of food products including seafood, meat, dairy, fruits, vegetables, nuts, chocolates, and fermented products. Foods containing proteins or amino acids in free form can have microbial or biochemical activity and BAs may be present.

Fermented products can contain BAs such as milk products, for example, cheese 5–4500 ppm, wines 5–135 ppm, beer 2.7–14 ppm. BAs can also be present in foods that are spoiled or in the beginning of spoilage such as fish and fish products 2300–5000 ppm, animal liver like beef about 330 ppm, processed meat and meat products 9–650 ppm [2]. BAs can be used in nonfermented products such as decomposition markers or indicator compounds. Deteriorated foods contain high amounts of BAs with the most abundant being cadaverine and putrescine. BAs contained in high amounts can have a serious health risk for consumers who belong to sensitive population. Symptoms may include hot flushes, respiratory discomfort, nausea, cold sweat, headaches, palpitations, red rash, low or high blood pressure. Alcohol consuming and presence of acetaldehyde may increase sensitivity to biogenic amines.

### **3. Safety issues and function**

Scombroid poisoning which is caused due to histamine presence is a very important issue that is why only histamine has a regulatory limit, according to EU regulation (maximum 200 mg/kg in fresh fish and 400 mg/kg in fish products

after enzyme treatment and maturation in brine). After fish, cheese is the next most commonly implicated food item associated with tyramine poisoning, so called "cheese reaction," related with its high content in aged cheeses. Other potential BAs, especially histamine and putrescine, are also present in milk-based fermented foods. Among the approaches useful to control the formation of BAs are the reduction of microbial growth through chilling and freezing or hydrostatic pressures, irradiation, controlled atmosphere packaging, or the use of food additives, etc.

Proteins and protein-like compounds such as alkaloids, hormones, and nucleic acids can be synthesized by precursors such BAs which contain nitrogen. BAs could probably affect organism in processes like body temperature regulation, nutrient intake, blood pressure decrease or increase. As far as plants are concerned, putrescine (diamine) and spermidine and spermine (polyamines) play important role in physiological processes, such as flowering, cell division, fruit development, and stress response. Spermine and spermidine are essential for growth, metabolism, and renovation, of almost all organs in the human body and important for high metabolic activity maintenance of the proper functioning and immunological gut system [3].

BAs are potential precursors for the formation of carcinogenic N-nitroso compounds. In lipid-containing foods, such as ham, bacon, at high temperature and in high water content, the carcinogenic compound N-nitrosopyrrolidine can be produced from spermidine or putrescine. BAs like putrescine, cadaverine, spermidine may play the role of free radical quenchers. Tyramine is regarded as a very good antioxidant, and its antioxidant capacity increases with its concentration. Free radical inhibition depends on amino and hydroxy groups. Spermine, for example, can regenerate tocopherol from tocopheroxyl radical through hydrogenic donor from amino group.

The radical formed binds lipid or peroxide radicals into lipid complexes. Some BAs contribute to the flavor and taste of food.

### **4. BAs analytical methods**

The analytical methods reported for identification and quantification of BAs are based on different types of chromatography: gas chromatography (GC), thin layer chromatography (TLC), and high-performance liquid chromatography (HPLC) combined with precolumn or postcolumn derivatization techniques. Aliphatic BAs do not have absorption bands in the UV-VIS region, hence simple spectrometric detectors cannot be applied [4, 5]. Analysis of BAs without prior derivatization includes ion-pair chromatography combined with octylamine or heptanesulfonate as ion-pair reagents. For BAs ion-pair separation in reversed-phase columns with C12-C18 aliphatic chains, phenyl residues bound to a silica core are efficient. HPLC procedures usually involve precolumn or postcolumn derivatization procedure. Chemical reagents that are usually used for BA analysis by postcolumn derivatization are mainly ninhydrin and o-phthalaldehyde and for precolumn derivatization the following reagents: dansyl and dabsyl chloride, fluorescein, benzoyl chloride, 9-fluorenylmethyl chloroformate [5].

### **5. Conclusion**

BAs are low-molecular-mass organic bases which occur in plant- and animalderived products. BAs in food can occur by free amino acid enzymatic decarboxylation and other metabolic processes. Usually, in the human body, amines contained in foods are quickly detoxified by enzymes such as amine oxidases or by conjugation; however, in allergic individuals or if monoamino oxidase (MAO) inhibitors

**5**

**Author details**

Proestos Charalampos

provided the original work is properly cited.

*Introductory Chapter: Current Knowledge on Biogenic Amines*

are applied, the detoxification process is disturbed and BAs accumulate in the body. Knowing the concentration of BAs is essential because they can affect human health, and also because they can be used as freshness indicators to estimate the

*DOI: http://dx.doi.org/10.5772/intechopen.84447*

degree of food spoilage.

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

Department of Chemistry, Laboratory of Food Chemistry, National

and Kapodistrian University of Athens, Athens, Greece

\*Address all correspondence to: harpro@chem.uoa.gr

*Introductory Chapter: Current Knowledge on Biogenic Amines DOI: http://dx.doi.org/10.5772/intechopen.84447*

*Biogenic Amines*

from amino group.

**4. BAs analytical methods**

BAs contribute to the flavor and taste of food.

after enzyme treatment and maturation in brine). After fish, cheese is the next most commonly implicated food item associated with tyramine poisoning, so called "cheese reaction," related with its high content in aged cheeses. Other potential BAs, especially histamine and putrescine, are also present in milk-based fermented foods. Among the approaches useful to control the formation of BAs are the reduction of microbial growth through chilling and freezing or hydrostatic pressures, irradiation, controlled atmosphere packaging, or the use of food additives, etc. Proteins and protein-like compounds such as alkaloids, hormones, and nucleic acids can be synthesized by precursors such BAs which contain nitrogen. BAs could probably affect organism in processes like body temperature regulation, nutrient intake, blood pressure decrease or increase. As far as plants are concerned, putrescine (diamine) and spermidine and spermine (polyamines) play important role in physiological processes, such as flowering, cell division, fruit development, and stress response. Spermine and spermidine are essential for growth, metabolism, and renovation, of almost all organs in the human body and important for high metabolic activity maintenance of the proper functioning and immunological gut system [3]. BAs are potential precursors for the formation of carcinogenic N-nitroso compounds. In lipid-containing foods, such as ham, bacon, at high temperature and in high water content, the carcinogenic compound N-nitrosopyrrolidine can be produced from spermidine or putrescine. BAs like putrescine, cadaverine, spermidine may play the role of free radical quenchers. Tyramine is regarded as a very good antioxidant, and its antioxidant capacity increases with its concentration. Free radical inhibition depends on amino and hydroxy groups. Spermine, for example, can regenerate tocopherol from tocopheroxyl radical through hydrogenic donor

The radical formed binds lipid or peroxide radicals into lipid complexes. Some

The analytical methods reported for identification and quantification of BAs are based on different types of chromatography: gas chromatography (GC), thin layer chromatography (TLC), and high-performance liquid chromatography (HPLC) combined with precolumn or postcolumn derivatization techniques. Aliphatic BAs do not have absorption bands in the UV-VIS region, hence simple spectrometric detectors cannot be applied [4, 5]. Analysis of BAs without prior derivatization includes ion-pair chromatography combined with octylamine or heptanesulfonate as ion-pair reagents. For BAs ion-pair separation in reversed-phase columns with C12-C18 aliphatic chains, phenyl residues bound to a silica core are efficient. HPLC procedures usually involve precolumn or postcolumn derivatization procedure. Chemical reagents that are usually used for BA analysis by postcolumn derivatization are mainly ninhydrin and o-phthalaldehyde and for precolumn derivatization the following reagents: dansyl and dabsyl chloride, fluorescein, benzoyl chloride, 9-fluorenylmethyl chloroformate [5].

BAs are low-molecular-mass organic bases which occur in plant- and animalderived products. BAs in food can occur by free amino acid enzymatic decarboxylation and other metabolic processes. Usually, in the human body, amines contained in foods are quickly detoxified by enzymes such as amine oxidases or by conjugation; however, in allergic individuals or if monoamino oxidase (MAO) inhibitors

**4**

**5. Conclusion**

are applied, the detoxification process is disturbed and BAs accumulate in the body. Knowing the concentration of BAs is essential because they can affect human health, and also because they can be used as freshness indicators to estimate the degree of food spoilage.

### **Author details**

Proestos Charalampos Department of Chemistry, Laboratory of Food Chemistry, National and Kapodistrian University of Athens, Athens, Greece

\*Address all correspondence to: harpro@chem.uoa.gr

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

### **References**

[1] Koutsoumanis K, Tassou C, Nychas G. Biogenic amines in foods. In: Juneja V, Sofos J, editors. Pathogens and Toxins in Foods. Washington, DC: ASM Press; 2010. pp. 248-274. DOI: 10.1128/9781555815936.ch16

[2] EFSA Panel on Biological Hazards (BIOHAZ). Scientific opinion on risk based control of biogenic amine formation in fermented foods. EFSA Journal. 2011;**9**:2393

[3] Linares DM, Río BD, Ladero V, Martínez N, Fernández M, Martín MC, et al. Factors influencing biogenic amines accumulation in dairy products. Frontiers in Microbiology. 2012;**3**:180. DOI: 10.3389/fmicb.2012.00180

[4] Erim FB. Recent analytical approaches to the analysis of biogenic amines in food samples. Trends in Analytical Chemistry. 2013;**52**:239-247

[5] Proestos C, Loukatos P, Komaitis M. Determination of biogenic amines in wines by HPLC with precolumn dansylation and fluorimetric detection. Food Chemistry. 2008;**106**(3):1218-1224

**7**

Section 2

Trends in Biogenic Amines

Analysis

## Section 2
