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Catechins: the Essence of Tea

Huafu Wang

FoodInfo Online Features 1 December 2002

http://www.ifis.org/library.html#ifis/11609
© IFIS Publishing 2005 - All Rights Reserved

R & D Department, William Ransom & Son plc, 104 Bancroft, Hitchin, Hertfordshire, SG5 1LY, UK. Tel. +44 1462 437615. Fax +44
1462 420528. E-mail hwang@williamransom.com

If you are cold, tea will warm you. If you are too heated, it will cool you. If you are depressed, it will cheer you. If you are excited, it
will calm you.

- William E Gladstone

1. Introduction

Tea is consumed throughout the world and, besides water, is the most popular beverage globally. The quality of tea is determined
principally by colour, taste and aroma of the leaves, as well as the infusions formed from them. The chemical composition of fresh tea
leaves (flush) is also of prime importance in determining the potential tea-making quality of tea, while techniques of tea manufacture
significantly influence the quality of tea in terms of the number of chemical constituents formed. Among these, tea catechins, which are
a type of polyphenol, can be regarded as a fundamental element of tea due to their high concentration in tea leaves and their
importance in determining the colour, taste and aroma, as well as the functional properties, of tea.

2. Types of tea

Tea can be roughly classified into three main types: green (unfermented), oolong (semi-fermented), and black (fully-fermented).
Green tea is made by inactivating the enzymes in the fresh leaves, either by firing or by steaming, to prevent the enzymatic oxidation
of tea catechins. Black tea is made by a polyphenol oxidase-catalysed oxidation of fresh leaf catechins, termed fermentation, which is
initiated by the processes of withering and rolling. Oolong tea is prepared by a variety of processes including firing, which is carried out
shortly after rolling and arrests fermentation halfway through the process. Therefore, oolong tea is also known as semi-fermented tea
and exhibits characteristics that are between black and green tea.

Other, less common, kinds of tea include white, yellow and dark teas, and scented and brick teas, which can be based on green, oolong
or black teas.

3. Chemistry of tea catechins

The main components of tea leaves are tea catechins, namely (—)-epigallocatechin gallate (EGCG), (—)-epigallocatechin (EGC), (—)-
epicatechin gallate (ECG) and (—)-epicatechin (EC) (Figure 1); these compounds represent 20-30% of the dry weight in fresh tea
leaves. Structurally, tea catechins are flavanols derived by the shikimic and acetate-malonate biosynthetic pathways, and are
characterised by their C6-C3-C6 skeletal structure which corresponds to 2-phenyl-substituted benzopyrans and pyrones (Nakabayashi
1991). Catechins are colourless, water-soluble compounds which impart bitterness and astringency to tea infusions.

Catechins are not unique to tea and have been found in red wines, apples, grapes and chocolate. However, tea is the only beverage
that has been found to contain (+)-gallocatechin (GC), EGC, ECG, and EGCG in addition to (+)-catechin (C) and EC (Arts et al. 2000).

Almost all characteristics of manufactured tea, including taste, colour and aroma, are associated directly or indirectly with changes to
tea catechins. Catechins may influence tea quality in several ways, as described below.

4. Oxidation in relation to the colour of tea

The colour of a black tea infusion is not actually black, but is bright orange, reddish or reddish brown. Black tea pigments are usually
divided into orange coloured theaflavins (TFs) and brown thearubigins (TRs). As shown in Figure 2, there are four main TFs in black
tea: theaflavin, theaflavin 3-gallate, theaflavin 3'-gallate, and theaflavin 3,3'-digallate. These are formed through oxidative
dimerisation between quinones derived from a simple catechin and a gallocatechin during the manufacture of black tea (Figure 3).
Galloyl ester groups of catechins can also be oxidised to form a benzotropolone skeleton, thereby producing a new type of tea pigment
(Wan et al. 1997). TRs are a heterogeneous group of phenolic pigments with relative molecular masses ranging from 700 to 40 000 Da
(Roberts 1962; Sanderson et al. 1972). They originate from further oxidative condensation via either C-O or C-C bond formation in
oxidative polymerisation reactions. TRs are formed by the oxidation of any one of the tea catechins or a combination thereof. It has
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been found that the amount of TRs increases with a corresponding decrease in TFs during fermentation of black tea, indicating that TFs
probably act as intermediates to TRs. The content of TFs in black tea is 0.3-2.0% on a dry weight basis (Balentine et al. 1997), while
the TR fraction comprises 10-20% of the dry matter of black tea (Sanderson 1972).

Different kinds of tea, even similar products from different areas, have different colour specifications. It is known that the content of
TFs and TRs and their relative proportions in black tea determine its colour: the higher the TF content, the brighter the tea infusion;
the higher the TR content, the browner the tea infusion (Chen et al. 2002). An inappropriate polymerisation between catechins and
other phenolic compounds can cause a dull appearance in the infused leaves. Moreover, undesirable colours in tea might indicate
potential problems associated with the flavour and aroma of the tea produced.

The yellow colour in green tea infusions is mainly determined by water-soluble flavonols which include kaempherol, quercetin and
myricetin, together with flavones and their glycosides, which have similar structures to catechins. The colour of green tea should be
either green or yellowish-green and should not contain any traces of red or brown colour such as that found in black tea; thus, catechin
oxidation should be avoided in green tea production. In addition, reactions between catechins and amino acids, as well as with sugars
in water at high temperature, should also be prevented as these produce yellowish-brown coloured substances which are undesirable in
green tea.

5. The flavour of tea

Taste and aroma both contribute to the flavour of tea infusions, with the four major sensory properties associated with tea being
astringency, bitterness, sweetness and umami (a brothy or savoury taste) (Teranishi 1989; Yamanishi 1990). The taste of different
types of tea is made up of a balance between these four basic properties. Although bitterness and astringency are unpleasant to most
consumers, the taste of both green and black teas should contain elements of astringency and bitterness as these represent overall
quality requirements. Nakagawa (1975) studied the contribution of green tea constituents to the intensity of the brew taste. He found
that the bitterness and astringency of the green tea brew were almost entirely caused by catechins and other phenolic compounds,
with molecular weight determining whether catechins are bitter or astringent. For example, ECG and EGCG were found to be both bitter
and astringent, while EGC, EC and C were bitter with a sweet aftertaste (Yamanishi 1995). Zhang et al. (1992) studied the astringent
taste of black teas and found significant positive correlations between astringency, total catechins, and some individual catechins.
Wang et al. (1998) investigated a range of green teas, and found that both the contents of total catechins and gallated catechins had
highly significant effects on the bitterness of green teas. The intensity of bitterness and astringency for catechins decreases in the
order ECG > EGCG > GCG > EC > EGC = GC > C, indicating that gallated catechins are more bitter and more astringent than non-
gallated ones. Complex interactions between caffeine and tea catechins account for the complexity of tea flavour. Generally speaking,
monomeric flavonoids are more bitter than they are astringent, and, as polymer size increases, compounds become more astringent
than bitter.

Excessive bitterness and astringency might make the flavour of tea undesirable, especially in Western countries where people are not
accustomed to intense bitter and astringent notes in tea, particularly in green tea. The following processes are commonly used to
remove or decrease astringent or bitter components found in tea.

5.1 Blending

Western countries habitually drink black tea with added milk and sugar. This imparts an increased flavour and makes the tea taste less
harsh since the TFs, TRs and catechins in black tea can bind to the casein in milk, resulting in less bitterness and astringency, while the
beneficial effects of these catechins and their oxidation products are not affected when ingested by the body (Hollman et al. 2001;
Leenan et al. 2000; van het Hof et al. 1998). For green tea, a pleasant brew with a rich flavour can be made if it is blended with other
herbal materials, such as ginseng or wolfberries.

5.2 Decaffeination

Caffeine is also a bitter compound which contributes significantly to the flavour of tea, particularly the ‘briskness’ of the tea brew. Its
content in tea ranges from 2.5 to 4.0% (Bokuchava and Skoboleva 1980). Decaffeination can result in the final beverage having a
milder taste than its caffeinated equivalent.

5.3 Tannase treatment

Tannase (EC 3.1.1.20) is an esterase that acts specifically on the ester bond between galloyl groups and gallated tea polyphenols.
Wang et al. (1998) found that after tannase treatment, the content of EGCG and ECG decreased greatly in a green tea infusion, and,
as a result, the bitterness of the infusion was reduced. It should be emphasised, however, that although this treatment is suitable for
removing the bitterness and astringency of tea, the functional properties of tea are reduced as a result of loss of bioavailability of these
polyphenols. Tannase treatment has also been used in the manufacture of instant tea in order to increase the extractability and cold
water solubility of tea compounds (Takino 1976).

Catechins can also indirectly affect the formation of tea aroma, one of the critical aspects of tea quality. Wang et al investigated the
relationship between catechins and aroma compounds during qimen (keemun) black tea manufacture. Figures 4 and 5 show the
changes of aroma compounds and catechins, respectively, during processing of tea. As can be seen, a decrease in catechin content is
associated with an increase in the content of total aroma compounds, especially monoterpene alcohols, which are regarded as being
very important to black tea flavour. Takeo et al. (1985) also found, in their study on the formation of aroma of oolong tea, that if
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catechins were removed, the formation of aroma compounds such as geraniol and linalool increased significantly. However, rapid
oxidation of polyphenols inhibited the formation of aroma compounds in tea leaves (Takeo 1981).

6. Epimerisation

As observed above, the oxidation of catechins is one of the main chemical changes that occur during black tea manufacture. However,
during production of green tea, oxidation is limited by inactivating the enzymes in freshly picked tea leaves by means of firing or
steaming. Accordingly, epimerisation (the conversion of the tea catechins to their corresponding isomers) can occur during the
production of black tea or green tea beverages (Kiatgrajai et al. 1982; Komatsu et al. 1993; Nakagawa 1967; Suematsu et al. 1992).
Figure 6 shows the possible products of epimerisation of EGCG. It is recognised that catechins undergo epimerisation at the C-2
position in a hot aqueous solution (Kiatgrajai et al. 1982; Nakagawa 1967); this was confirmed by Seto et al. (1997) through 1H- and
13
C-NMR and optical rotation analysis. Epimerisation at the C-3 position only occurs when oxidative degallation is taking place (Coggon
et al. 1973).

Although individual catechins can undergo epimerisation at high temperatures, in green tea infusions, the predominant change appears
to be epimerisation from the epi-structure to the alternative diastereomer. Wang et al. (2001) found that this epimerisation takes place
more easily in tap water than in purified water. The complexity of the ions present in tap water, together with the difference in pH
between tap and purified water, are thought to be the main influential factors. In an infusion brewed with tap water, catechins are
easily epimerised and then rapidly degraded. Stability studies on catechins in strong green tea infusions prepared with a mixture of
ethanol and purified water at a ratio of tea leaves to solvent of 1:5 (w/v) have shown epimerisation at 40°C after a few days of
storage. Therefore, it is thought that not only temperature but also heating time influences epimerisation of catechins in green tea
infusions.

At ambient temperature in an aqueous solution, the main change is degallation of catechins, while at elevated temperature,
epimerisation becomes the predominant reaction. However, powdered catechins are usually quite stable; neither degradation nor
epimerisation is observed. Among catechins, stability decreases in the order C > EC > ECG > EGCG > EGC.

7. Complex formation

Tea cream and tea scum can often be observed after a cup of black tea is made. Tea cream is defined as the precipitate formed when a
black tea infusion cools and is a complex of mainly TFs, TRs, ester-type catechins (EGCG, ECG) and caffeine (Zhao and Jiang 2000).
Complex formation between TFs and caffeine results in an orange-yellow colour, while the complexes between TRs and caffeine are
dark reddish brown. Therefore, the ratio of TFs to TRs can influence the colour of ‘creamed down’ teas. It was found that binding of
caffeine to TRs was weaker than binding of caffeine to TFs (Cloughley 1981).

TFs and TRs can also influence the colour of black tea infusions by complexing with aluminium in the infusion, resulting in a more red
coloured infusion. In hard water areas, an unsightly film called tea scum or tea scale forms on the surface of the tea infusion,
irrespective of the type of tea used. The mechanism of tea scum formation involves aerial oxidation of tea polyphenolic components
such as catechins, TFs and TRs (Spiro and Juganyi 1994).

The content of individual catechins has been observed to decrease following the addition of milk to black tea, as consumed in Western
countries; for EGCG, GCG and ECG, the decreases were 70, 65, and 70.4%, respectively (Wang et al. 2001). Proteins in the milk are
thought to be the main reason for this decrease. The mechanism for binding of catechins to milk proteins derives from the fact that
catechins are multidentate ligands able to bind simultaneously (via different phenolic groups) at more than one point to the protein
surface. It appears that the active sites required to precipitate proteins are a galloyl group and a di- or trihydroxyl-phenyl group. Both
ECG and EGCG have two such active sites per molecule.

8. Antioxidant properties of tea

Catechins are not only important quality contributors to tea but also have important bioactive (functional) properties. Catechins have
been shown to have antibacterial, anti-inflammatory, antiallergic, antithrombotic, and vasodilatory activities. These properties are
thought to be related to their antioxidative activity. However, individual catechins differ in their chemical or biological activities
according to the concentrations and the media used. It is generally accepted that galloyl esters of catechins are more active than non-
galloylated catechins because they have lower redox potentials (Balentine et al. 1997). The antioxidant activity of epicatechin is
increased with the addition of another hydroxyl group on the B ring (forming epigallocatechin) and is further increased with the
addition of gallic acid (forming epigallocatechin gallate) on the C ring, to the point where it is equivalent to quercetin which is an
effective antioxidant.

9. Abbreviations

C: (+)-catechin
EC: (—)-epicatechin
GC: (+)-gallocatechin
EGC: (—)-epigallocatechin
ECG: (—)-epicatechin gallate
GCG: (+)-gallcatechin gallate
EGCG: epigallocatechin gallate
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NMR: nuclear magnetic resonance
TFs: theaflavins
TRs: thearubigins

10. Acknowledgements

The author would like to thank Mrs Evelyn Chesmar for her assistance in the preparation of this paper.

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van het Hof, K. H., Kivits, G. A. A., Weststrate, J. A. and Tijburg, L. B. M. 1998. Bioavailability of catechins from tea: the effect of milk.
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oxidation of epicatechin gallate and isolated from tea. Journal of the Science of Food and Agriculture 74: 401-408.

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Meeting of LSSCB, 24-25 July 1998: 58-59. Cambridge, UK.

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food components. In: Proceedings of European Conference on Bioactive Compounds in Plant Foods – Health effects and Perspectives
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Zhang, D., Kuhr, S. and Engelhardt, U. H. 1992. Influence of catechins and theaflavins on the astringent taste of black tea brews.
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across the Taiwan Straits, April 26-29 2000: 80-85. Fuzhou, China.

12. Further reading

Dufresne, C. J. and Farnworth, E. R. 2001. A review of last research findings on the health promotion properties of tea. Journal of
Nutritional Biochemistry 12: 404-421.

Liao, S., Kao, Y. H. and Hiipakka, R. A. 2001. Green tea: biochemical and biological basis for health benefits. Vitam Horm 62: 1-94.

Yang, C. S., Maliakal, P. and Meng, X. 2002. Inhibition of carcinogensis by tea. Annual Review of Pharmacology and Toxicology 42: 25-
54.

About the author

Huafu Wang, BSc, MSc, has been involved in tea research for over 20 years and has a particular interest in separation, application and
analysis of tea components. He is an Honorary Professor at the Tea Research Institute, Chinese Academy of Agricultural Sciences, and
has been a committee member of the Chinese Tea Association. Huafu Wang joined the R & D department of William Ransom & Son plc
in February 1998 and has published over 50 research papers and reviews in the field of tea chemistry and biochemistry.
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Figure 1. Chemical structures of tea catechins and their epimers.

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Figure 2. Structures of theaflavins in black tea.

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Figure 3. Polyphenol oxidation during black tea manufacture.

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Figure 4. Production of aroma components during black tea manufacture.

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Figure 5. Degradation of catechins during black tea manufacture.

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Figure 6. Possible products of epimerisation of EGCG.