Acylated Anthocyanin-A Review
Acylated Anthocyanin-A Review
Anna B¹kowska-Barczak
Key words: acylated anthocyanins, intramolecular copigmentation, natural food colorants, red cabbage, black carrot
     There is a demand for food colorants from natural sources that can serve as alternatives to the use of synthetic dyes due to the consumer con-
cerns over the use of synthetic additives. Documented health benefits of anthocyanin extracts intensified the interest in anthocyanin-rich food.
Anthocyanins, between other benefits, are potent antioxidants and may be useful to cure noninsulin-dependent diabetes.
     The finding that anthocyanin pigments containing acyl substituent are incredibly stable opens new opportunities for food producers. The sta-
ble acylated anthocyanins are present in large amounts in vegetables such as: red cabbage, black carrot, red radish, red potatoes or red corn. These
pigments indicate a low sensibility to pH changes and an increased heat and light stability. For this reason, acylated anthocyanins are suitable to
be applied not only for food with low pH but also for neutral and slightly alkaline products (dairy products, powdered and ready-to-eat desserts).
INTRODUCTION R
Author’s address for correspondence: Anna B¹kowska, Department of Fruit, Vegetable and Cereals Technology, Agricultural University of Wro-
c³aw, ul. Norwida 25, 50-375 Wroc³aw, Poland; tel.: (48 71) 320 54 74; fax: (48 71) 320 54 77; e-mail: annab@star.ar.wroc.pl
108                                                                                                                                                A. B¹kowska-Barczak
                                               OH
                                                                                                                  O                                 O
                                                             OH
                                                                                            HO                                                                               OH
                                    +                                                                                                         HO
              HO                    O                                                                                 OH
                                                             OH
                                                                                                 O                                                      OH           O
                                              HO
                                         O                                                            succinic acid                                     malic acid
 HO                                                               OH
                            O                       O
                     OH
                 O                                                     OH
                                                                                                  O          O
HO                                                                                                                               O
            OH                                                                                                                                 OH       HO
                                                                  O
                                                                                            HO                   OH        HO
                                                                                                                                                                         O
                                                                                    OH                                               O
                                                                  O
                                                                            O
                                                                                                 malonic acid                   oxalic acid                  acetic acid
FIGURE 2. Chemical structure of delphinidin-3-malonylglucoside-5-                        FIGURE 4. Common aliphatic acid acylated with sugar moieties of
-glucoside isolated from flowers of Scutellaria baicalensis G [Oszmiañ-                  anthocyanins.
ski et al., 2004].
    It is generally recognized that light accelerates degrada-                 is offset by a high tinctorial strength. Available in a liquid or
tion of anthocyanins. This adverse effect has been demon-                      sprayed-dried form, the extracts are water-soluble and,
strated in several fruit juices and red wines. In fruit juices it              because of the presence of acylated anthocyanins, demon-
has been established that acylated anthocyanins are more                       strate improved stability to heat and light [Giusti, 2002].
stable than unacylated derivatives [Inami et al., 1996]. In                    Slight changes in pH have a large effect on the resulting
addition, the absorbance of juices tested was observed to                      hue, and therefore, pH control of the final product becomes
increase after exposure to light. Further investigations                       crucial.
demonstrated that anthocyanins containing cinnamoyl                                 The commercialization of red cabbage anthocyanins was
derivatives are able to isomerize from trans to cis form                       pioneered by the Overseal Natural Ingredients Ltd under
[George et al., 2001; Yoshida et al., 1990, 2000, 2002, 2003 a,                their brand name MagentoTM [http://www.overseal.co.uk].
b]. The reaction of isomerization evokes colour intensifica-                   The interest in and success of red cabbage–derived antho-
tion and resistance to pyrilium ring hydration.                                cyanins lie in the fact that they: produce a bright pink shade
    High temperature is another factor inducing degrada-                       at low pH on clear bases and pink/mauve shades in white
tion of anthocyanin colorants [B¹kowska et al., 2003; Fur-                     bases; provide mauve/blue shades at more neutral pH val-
tado et al., 1993; Garcia-Viguera et al., 1999; Horuba³a,                      ues; have no unpleasant taste due to minimized odour
1996]. The results presented by Dyrby et al. [2001] showed                     notes; demonstrate superior stability to heat and light over
that acylated anthocyanins from red cabbage were more sta-                     anthocyanins from more traditional sources such as grape-
ble than the unacylated anthocyanins obtained from red                         skin and elderberry; are naturally low in polyphenols redu-
grape, black currant and elderberry. The high stability of                     cing the risk of hazing with proteins; are available all year
red cabbage anthocyanins during heating at 80°C was con-                       round; and demonstrate potential health benefits when
firmed by our unpublished data.                                                included into the diet [http://www.overseal.co.uk].
                                                                                    Giusti and Wrolstad [2003] tested the viability of using
ACYLATED ANTHOCYANINS AS COLORANTS FOR                                         acylated anthocyanins from red cabbage to colour of dairy
THE FOOD INDUSTRY                                                              products such as yogurt or sour cream, with pH levels of
                                                                               about 4.2–4.5. These anthocyanins gave an attractive purple
     The confirmed large stability of anthocyanins, including                  colour, resembling the colour of blueberries.
acidic substituent, and their wide colour range caused that                         Other excellent source of acylated anthocyanins is black
searches for acylated anthocyanin-rich material have begun.                    carrot (Daucus carota L). It has been grown and consumed
     Taking into consideration low prices, big surface of                      in the East for at least 3,000 years. Historical records indi-
tillage and high amounts of anthocyanins, red cabbage                          cate that it was cultivated in parts of Europe in the 12th cen-
(Brassica oleracea L) is the most valuable source of the sta-                  tury and in Holland by the 14th century. It was commonly
ble form of anthocyanins for the Polish food industry. Red                     consumed until about 1750 when Dutch breeders developed
cabbage contains about 15 anthocyanins (mostly diacylated)                     the orange variety which we are all familiar with [Pszczola,
being derivatives of cyanidin-3-diglucoside-5-glucoside acy-                   1999]. The black carrot is still consumed in some parts of
lated with ferulic, sinapic and/or p-coumaric acids (Figure                    the world, such as Spain, Pakistan, Afghanistan, Turkey, and
6) [Baublis et al., 1994; Giusti et al., 1999; Mazza & Miniati,                Egypt. Nowadays black carrots are also cultivated in Europe
1993; Murai & Wilkins, 1990].                                                  (including Poland) on a large scale.
     The extract of red cabbage anthocyanins is one of the                          The colour of this vegetable is determined by 5 main
most expensive anthocyanin concentrates, but its high cost                     anthocyanins, being derivatives of cyanidin-3-rutynoside-
                                                                               -glucoside-galactoside acylated with one cinnamic acid (p-
                                        OH
                                                                               -coumaric, ferulic or sinapic) (Figure 7) [Dougall et al., 1997,
                                             OH                                1998; Gakh et al., 1998; Giusti, 2002; Giusti & Wrolstad,
                                                                               2003; Glässgen et al., 1992; Kammerer et al., 2004; Lazcano
                  HO        O+
                                                  R4                OH         et al., 2001; Narayan & Venkatarman, 2000]. It was the GNT
                                                           O                   group that pioneered the development of food colorants
 HO                                          O                            OH
                                   O                                           from black carrot [Pszczola, 1999]. The coloring extract sold
 HO           O                                            OH                  under EXBERRY® brand name is pleasantly fruity in taste
                       O                                                 OH
        HO                         R2            O
                                                                    OH         and free of off flavours. The black carrot extract is also pro-
                  OH         R10                                               duced by the Overseal Foods Ltd under its brand name
                                                                O
                                                                               Carantho® [Downham & Collins, 2000]. EXBERRY® and
                              R3                                               Carantho® extracts offer the following features and bene-
                                                                               fits: they provide an excellent bright strawberry red shade in
                                                       O
                                                                               acidic products, up to pH 4.5; they exhibit mauve to blue
                                                                               tones under neutral pH conditions; they are an excellent
1.    R1 = R2 = R3 = R4 = H
                                                                               vegetarian and kosher alternative to carmine; they contain
2.    R1 = R3 = R4 = H    R2 = OCH3
                                                                               low levels of polyphenols, which are naturally present in
3.    R1= R4 = H          R2 = R3 = OCH3
4.    R1 = R2 = R3 = H    R4 = sinapic acid
                                                                               grapeskin anthocyanins and which can cause hazing and pre-
5.    R1 = R3 = H         R2 = OCH3         R4 = sinapic acid                  cipitation problems; and finally they offer improved stability
6.    R1 = H              R2 = R3 = OCH3 R4 = sinapic acid                     to heat, light and SO2 [http://www.overseal.co.uk].
                                                                                    Other permitted sources of stable acylated anthocyanins
FIGURE 6. Chemical structure of main acylated anthocyanins from                are also under evaluation. One of them is red radish (Ra-
red cabbage (Brassica oleracea) [Mazza & Miniati, 1993].                       phanus sativus L). This vegetable contains 12 acylated
Acylated anthocyanins                                                                                                                               111
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Acylated anthocyanins                                                                                             115
Anna B¹kowska-Barczak
    Wraz ze wzrostem œwiadomoœci konsumentów roœnie ich zainteresowanie produktami spo¿ywczymi, które oprócz
zaspokojenia g³odu, spe³niaj¹ dodatkowe funkcje fizjologiczno-¿ywieniowe, wp³ywaj¹c na poprawê zdrowia lub zapobie-
gaj¹c chorobom takim jak: nowotwory, cukrzyca, mia¿d¿yca, nadciœnienie czy próchnica. Te szczególne potrzeby kon-
sumentów zmuszaj¹ producentów ¿ywnoœci do rezygnacji ze stosowania barwników syntetycznych i zastosowania natural-
nych, aktywnych biologicznie barwników, m.in. antocyjanowych, do barwienia ¿ywnoœci. Zwi¹zane to jest jednak ze
znacznymi ograniczeniami, gdy¿ naturalne barwniki antocyjanowe s¹ zwi¹zkami bardzo niestabilnymi. Odkrycie antocy-
janów acylowanych o du¿ej stabilnoœci budzi nadziejê, ¿e barwniki te nadadz¹ po¿¹dany, trwa³y kolor produktom ¿ywnoœ-
ciowym. Wysoka stabilnoœæ barwników acylowanych zwi¹zana jest z utworzeniem kompleksu w formie „kanapki”, który
os³ania cz¹steczkê przed hydratacj¹ w pozycji C-2 i C-4. Kompleks ten powstaje w wyniku utworzenia wi¹zania pomiêdzy
reszt¹ aromatyczn¹ grupy acylowej a pierœcieniem pyryliowym kationu flawyliowego (rys. 5).
    Antocyjany acylowane wystêpuj¹ w wielu kwiatach, owocach i warzywach, jednak zastosowanie w przemyœle mo¿e
znaleŸæ jedynie kilka z nich. S¹ to: czarna kapusta zawieraj¹ca w wiêkszoœci poliacylowane antocyjany (rys. 6), czarna
marchew (zawieraj¹ca pojedynczo acylowane antocyjany (rys. 7), czerwona rzodkiewka czy czerwona kukurydza. Preparaty
acylowanych antocyjanów otrzymane z wymienionych surowców cechuj¹ siê ma³¹ wra¿liwoœci¹ na zmiany pH, wysok¹ sta-
bilnoœci¹ podczas ogrzewania i naœwietlania oraz ma³¹ zawartoœci¹ polifenoli, dziêki czemu dodatek tych preparatów do
produktów zawieraj¹cych bia³ka nie powoduje zmêtnieñ.
    Te wyj¹tkowe zalety preparatów antocyjanów acylowanych stwarzaj¹ realne nadzieje na wykorzystanie ich do barwienia
produktów o obojêtnym lub lekko zasadowym odczynie, jak produkty mleczne, desery w proszku czy polewy lukrowe.