Elsevier

Phytochemistry

Volume 64, Issue 5, November 2003, Pages 923-933
Phytochemistry

Review
Analysis and biological activities of anthocyanins

https://doi.org/10.1016/S0031-9422(03)00438-2Get rights and content

Abstract

Anthocyanins are naturally occurring compounds that impart color to fruits, vegetables, and plants. They are probably the most important group of visible plant pigments besides chlorophyll. Apart from imparting color to plants, anthocyanins also have an array of health-promoting benefits, as they can protect against a variety of oxidants through a various number of mechanisms. However, anthocyanins have received less attention than other flavonoids, despite this. This article reviews their biological functions and pre-clinical studies, as well as the most recent analytical techniques concerning anthocyanin isolation and identification.

Anthocyanins are naturally occurring compounds imparting color to plants, and are probably the most important group of visible plant pigments besides chlorophyll. Furthermore, they also contain an array of health-promoting benefits. However, anthocyanins have received less attention than other flavonoids, despite their far-reaching effects. In this paper, the biological functions, pre-clinical studies, and the most recent analytical techniques for anthocyanin isolation and identification were reviewed.

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Introduction

Anthocyanins (in Greek anthos means flower, and kyanos means blue) are the more important plant pigments visible to the human eye. They belong to the widespread class of phenolic compounds collectively named flavonoids. They are glycosides of polyhydroxy and polymethoxy derivatives of 2-phenylbenzopyrylium or flavylium salts (Fig. 1).

The differences between individual anthocyanins relate to the number of hydroxyl groups, the nature and number of sugars attached to the molecule, the position of this attachment, and the nature and number of aliphatic or aromatic acids attached to sugars in the molecule. To date, there are 17 known naturally occurring anthocyanidins or aglycones which are listed in Tables 1. The role of anthocyanidins in plants is summarized in Tables 2.

Only six anthocyanidins are common in higher plants—pelargonidin (Pg), peonidin (Pn), cyanidin (Cy), malvidin (Mv), petunidin (Pt) and delphinidin (Dp). The glycosides of the three non-methylated anthocyanidins (Cy, Dp and Pg) are the most widespread in nature, being present in 80% of pigmented leaves, 69% of fruits and 50% of flowers. The distribution of the six most common anthocyanidins in the edible parts of plants is cyanidin (50%), pelargonidin (12%), peonidin (12%), delphinidin (12%), petunidin (7%), and malvidin (7%). The following four classes of anthocyanidin glycosides are common: 3-monosides, 3-biosides, 3,5-diglycosides and 3,7-diglycosides. 3-glycosides occur about two and half times more frequently than 3,5-diglycosides. So, the most widespread anthocyanin is cyanidin 3-glucoside.

Based on several reviews to date, it is estimated that more than 400 anthocyanins have been found in nature. In the book entitled “Anthocyanins in Fruits, Vegetables, and Grains” (Mazza and Miniah, 1993), 258 anthocyanins are listed; and according to the reviews of Harborne & Williams, 1998, Harborne & Williams, 2001, from January 1995 to December 1997, 85 new anthocyanins were recorded, whilst from January 1998 to December 2000, some 50 new anthocyanin pigments were found in plants.

Section snippets

Recent advances in anthocyanin analysis and identification

Anthocyanins are soluble in polar solvents, and they are normally extracted from plant materials by using methanol that contains small amounts of hydrochloric acid or formic acid. The acid lowers the solution's pH value and prevents the degradation of the non-acylated anthocyanin pigments. However, as hydrochloric acid or formic acid is concentrated during the evaporation of the methanol-hydrochloric acid or methanol-formic acid solvent, pigment degradation occurs (e.g. in the extract of Azalea

Functions of anthocyanins

The most significant function of anthocyanins is their ability to impart color to the plants or plant products in which they occur. They play a definite role in the attraction of animals for pollination and seed dispersal, and hence they are of considerable value in the co-evolution of these plant-animal interactions. Anthocyanins and 3-deoxyanthocyanidins however have roles in flowering plants other than as attractants. They can act as antioxidants, phytoalexins or as antibacterial agents.

Biological activities of anthocyanins

Anthocyanins also possess known pharmacological properties and are used by humans for therapeutic purposes. Following the recognition that pigment extracts are more effective than O-(β-hydroxyethyl) rutin in decreasing capillary permeability and fragility and in their anti-inflammatory and anti-oedema activities (Wagner, 1985), it is possible that anthocyanins may replace rutin and its derivatives in the treatment of illnesses involving tissue inflammation or capillary fragility. The crude

Antioxidant properties and free radical scavenging properties

In 1994, Tsuda et al. reported the antioxidant activity of the anthocyanin pigments cyanidin 3-O-β-glucoside (C3G) and cyanidin (Cy), which was examined by using linoleic acid autoxidation, liposome, rabbit erythrocyte membranes, and rat liver microsomal systems. C3G and Cy had antioxidative activity in all systems. Cy had a stronger activity than C3G and the same activity as α-tocopherol in the liposome and rabbit erythrocyte membrane systems. In the rat liver microsomal system, Cy and C3G

The interaction with DNA

A study of the inter-reaction of anthocyanins and DNA was carried out by Sarma and Sharma (1999). They found that calf thymus DNA (ctDNA) and cyanidin can form a cyanidin–DNA copigmentation complex, which displayed a 15–20 nm bathochromic shift when cyanin is mixed with calf thymus DNA (ctDNA). Exposure of either cyanidin or ctDNA individually to hydroxyl radicals (OH) obtained in a Fenton reaction caused severe oxidative damage. However, formation of the cyanin-DNA complex prior to exposure to

Conclusions

Anthocyanins represent a class of important antioxidants, as they are so common in human foods. In recent years, many papers have been published on the in vitro antioxidant activity of anthocyanins and their other functions, as well as studies assessing the correlation between their antioxidant capacity and chemical structure. However, there are still fewer studies compared to studies of other flavonoids. The antioxidant efficacy in vivo of anthocyanins has also been less thoroughly documented,

Acknowledgements

The research was supported by Nanyang Technological University Research Grant No. RP3/99 CLS. We thank the Nanyang Technological University and the Lee Foundation for their financial support.

Jin-Ming Kong obtained his BSc degree in 1985 from Department of Chemistry, Zengzhou University, People's Republic of China, and MSc degree in 1992 from School of armaceutical Sciences, Beijing Medical University, People's Republic of China. After working in an institute for cosmetics study for several years in Beijing, he entered Nanyang Technological University, Singapore, to conduct the research on the flavonoids and anthocyanins in 1998. He was conferred PhD degree in 2002.

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    Jin-Ming Kong obtained his BSc degree in 1985 from Department of Chemistry, Zengzhou University, People's Republic of China, and MSc degree in 1992 from School of armaceutical Sciences, Beijing Medical University, People's Republic of China. After working in an institute for cosmetics study for several years in Beijing, he entered Nanyang Technological University, Singapore, to conduct the research on the flavonoids and anthocyanins in 1998. He was conferred PhD degree in 2002.

    Lian-Sai Chia obtained his BSc degree in Chemistry from Nanyang University, Singapore, and MSc and PhD degrees in chemistry from the University of British Columbia, Canada. From 1972 to 1974, he was a recipient of the International Nickel Company graduate research fellowship. He was the Head of Science Department in the Institute of Education, Singapore, from 1980 to 1984. His research interests include chemistry of bioactive compounds (e.g. antioxidants, flavonoids, phenolics), environmental chemistry, sonochemistry, and learning strategies/instructional design in chemistry/science.

    Ngoh-Khang Goh obtained his first degree in Chemistry from Nanyang University in 1964. He was then awarded a PSC Overseas Scholarship to pursue his postgraduate studies in Germany, at the University of Muenster, under the “German Academic Exchange Service” scheme, and completed his studies with both 1st Class Master and Doctorate degrees. From 1991 to 2000 he was the Head of the Chemistry Division in the National Institute of Education, Nanyang Technological University. Presently he is the Deputy Head of the Science and Technology Education Academic Group in the same institute. His research interests include herbal chemistry, environmental chemistry, materials science, instructional design in chemistry/science and process skills learning.

    Tet-Fatt Chia obtained his BSc (Hons), MSc and PhD degrees from the National University of Singapore, and his PGDipTHE from Nanyang Technological University. He specializes in the study and usage of molecular genetics on different life forms, especially those in plants. His major thrust is to study and understand the workings and functions of DNA, genes and proteins and its usage in agriculture and medicine. In orchid research, he has produced the world's first transgenic glowing Dendrobium orchid flower, by successfully transforming the orchid cells with the firefly luciferase gene and tracking its growth, development and gene expression. He has also developed tissue-printing techniques for virus identification and eradication. Physiological and molecular studies have shown that virus-free orchids have not only higher photosynthesis but also different translocation pattern from the diseased plants. Also, he has identified DNA genetic markers for trait prediction like flower size and inflorescence length. Another area of his research is in preventive medicine. He has genetically altered plants to produce novel compounds with medicinal properties. His latest breakthrough is the genetic engineering of resveratrol producing red lettuce, for prevention against cancer and heart diseases. He is currently pursuing this area (preventive medicine) of research and is working on a number of compounds with medicinal properties.

    R. Brouillard is Professor of Chemistry at the University Strasbourg I. He graduated from the Faculty of Sciences in Paris where he earned his PhD degree in 1974. After postdoctoral work at Reading under the guidance of Professor J.B. Harborne, he was promoted to full Professor at Strasbourg University. Since then he has been Head of the laboratory of Polyphenol Chemistry. His major lines of research concern plant pigmentation, molecular interactions, metal complexation and biological activities of flavonoids. Specific works include covalent and non-covalent interactions of polyphenols with a range of compounds, anthocyanin colour stabilisation and variation, both in vitro and in vivo, organic synthesis, analytical detection methods for small and large bio-compounds, investigation of reaction mechanisms using relaxation techniques, NMR and other spectroscopies. At a more applied level, he did a lot of work on wine anti-oxidant properties and stilbenes' chemio-preventive health effects, for instance. In particular, he pointed out for the first time, a unique molecular structural feature accounting for red wine ageing process. His studies of synthetic, natural or artificial, colorants were useful to the textile and cosmetic industries. Over the past decade, he established many collaborations with the industry. He is author, or co-author of more than one hundred papers.

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