Polyphenol Interactions and Food Organoleptic Properties

Susana Soares, Nuno Mateus, and Victor de Freitas, Faculdade de Ciências da Universidade do Porto, Porto, Portugal
© 2018 Elsevier Inc. All rights reserved.

Introduction 1
Polyphenols 1
Interactions Between Polyphenols and Other Food Compounds 2
Interaction With Food Lipids 2
Interaction With Food Carbohydrates 2
Interaction With Proteins 4
Food Proteins 4
Salivary Proteins 5
Concluding Remarks 5
References 6

Introduction

Polyphenols are present in all vegetables, fruits and derived foodstuffs, e.g. coffee, beer, tea and wine. These compounds are referred
as the phytonutraceuticals of the century due to important biological properties linked to their intake, e.g. cardiovascular protection
and antioxidant activity (Valavanidis and Vlachogianni, 2013).
Besides health-promoting properties, polyphenols are also associated with some sensory properties of foodstuffs, namely colour
and taste. Regarding colour, anthocyanins are one of the most important natural pigments but they present a problem due to their
high instability. Regarding taste, polyphenols are responsible for some unpleasant organoleptic properties, namely astringency and
bitterness. Astringency is a tactile sensation defined as dryness, tightening and puckering sensations perceived in the oral cavity
during the ingestion of astringent molecules, mainly tannins, alums and some metal ions. It is desired if these molecules are in
balanced levels for some food products such as red wine, being a parameter of wine quality, but it is unpleasant when perceived
in excess. Currently, oral astringency onset is mainly explained by the precipitation of salivary proteins by tannins. Bitterness is
a taste and so it is perceived via activation of specific bitter taste receptors (TAS2Rs) by some polyphenols. Usually, excessive bitter-
ness is also undesirable.
Polyphenols are widely known to interact with many different compounds, both with food compounds, such as carbohydrates,
lipids and proteins, as well as with biological compounds, namely proteins. Interactions between polyphenols and molecules from
food are mostly based on non-covalent hydrophobic interactions but in the cases of interactions between polyphenols and proteins
or/and carbohydrates, hydrogen bonds also contribute significantly. Furthermore, some covalent bonds may also occur under
certain food processing conditions. All these interactions can influence the overall sensory perception of foodstuffs and consumer
acceptance. This article revisits the current knowledge about these interactions at a molecular level, how these interactions could
affect the sensory properties, e.g. taste, colour, texture, with the purpose to modulate them toward increasing consumer acceptance
and intake of healthy foodstuffs rich in polyphenols.

Polyphenols

Polyphenols are usually divided into two major groups: flavonoids and non-flavonoids. Flavonoids share a common flavanic core
(Fig. 1) and are further divided into several classes such as flavanols [(epi)catechin], flavonols (e.g. myricetin and quercetin),
anthocyanins (e.g. malvidin-3-glucoside), flavanones, flavones and isoflavones; non-flavonoid compounds include phenolic acids,

Figure 1 Structure of the flavanic core common to flavonoids.

1
2 Polyphenol Interactions and Food Organoleptic Properties

phenols and stilbenes. These classes differentiate according to the degree of unsaturation and degree of oxidation of the heterocyclic
pyranic ring C (Fig. 1). Flavonoids are the most relevant and widely present polyphenols in the human diet (2/3 of ingested
polyphenols are flavonoids) (Scalbert and Williamson, 2000). Among flavonoids, the most consumed groups are flavanols and
anthocyanins (Rasmussen et al., 2005).
Flavanols differ in the stereochemistry of C3 of ring C and pattern of hydroxylation of ring B (Fig. 1). They share a structural unit
of (epi)catechin and can range from monomers to polymers (proanthocyanidins). Conversely to other flavonoids classes, flavanols
usually occur as aglycone molecules without sugar molecules.
Anthocyanins are the main pigments in many flowers and fruits (e.g. grapes) responsible for the great diversity of colours (i.e.
red, violet and blue) found in nature and in some foodstuffs. In aqueous solution, the colour of anthocyanins is dependent on their
structure and also strongly affected by the pH (Brouillard and Lang, 1990). At acidic pHs (pH1), anthocyanins are present in their
flavylium cation form which has a red colour. As the pH increases, anthocyanins can be present in other different forms yielding
from the violet quinonoidal base to the non-coloured hemiketal form or to the trans-chalcone forms which present a yellow colour
(Pina, 1998).
Another common designation to some polyphenols is tannins. Tannins comprise a group of usually structural complex
polyphenols that share the ability to interact with proteins. Tannins are usually divided in two major subgroups: condensed and
hydrolysable tannins. Condensed tannins (proanthocyanidins) are polymers of flavanols, usually gallo- or (epi)catechin units,
which can form very complex and high-molecular weight structures. Hydrolysable tannins are further divided into gallotannins
and ellagitannins. They are esters of gallic acid or hexahydroxydiphenic acid, respectively, with a polyol, usually glucose.
In summary, polyphenols present a high structural diversity and possess a significant number of hydroxyl groups and planar
rings, which makes them susceptible to a wide range of interactions. Therefore, polyphenols can interact with one another and
with other types of molecules that surround them.

Interactions Between Polyphenols and Other Food Compounds

Lipids, proteins and carbohydrates are major food compounds often found together with polyphenols in the same food matrices.
An excellent review on these interactions and their biological effects was published by Jakobek (2015). Herein, these interactions
will be focused on a sensory perspective.

Interaction With Food Lipids

Lipids affect flavour perception by their effects on aroma, taste and mouthfeel. Surprisingly, only a few studies have investigated the
effect of dietary lipid–polyphenol interactions on taste. Dietary fats go through a digestion process that starts with mastication in
which lipids are often transformed into emulsions. The particle size of fat droplets present in these emulsions is important since it
influences the rheological properties, texture, shelf life and appearance (Dapcevic HadnaCev et al., 2013). The association of poly-
phenols with milk fat globules has been widely studied. Several studies have been focused on the interaction associated with tea
catechins and this interaction as shown to affect the size and the surface properties of milk fat globules (Rashidinejad et al.,
2016). In general, the globules seem rougher and larger in size in the presence of catechins, and sharp and rough particles are known
to cause more friction than rounder particles (De Wijk and Prinz, 2006).
Considering dietary lipids, it is inevitable to refer oxidation, which is an expected process in fat rich products, such as olive oil,
leading to deterioration that can become more pronounced during oil storage. Initially, lipids are radically oxidized to hydroper-
oxides, which are odourless and tasteless. However, cleavage of these products gives rise to various volatile compounds, known as
secondary oxidation products, which are responsible for typical unpleasant sensory characteristics of fat-rich foodstuffs. Oxygen,
light, temperature, metals, pigments, unsaturated fatty acid composition, as well as the quantity and kind of natural antioxidants,
are all factors that can influence the free radical mechanism of the autoxidation process but in a different manner. The addition of
phenolic extracts to olive oil to improve oxidative stability is not straightforward as expected, especially in the presence of hydro-
colloids, where their interactions with hydrocolloids can exert a significant influence and lead to different creaming rates, turbidity
and rheological behaviours, but can also have pro-oxidant effects under certain conditions (Caporaso et al., 2016). Shishikura et al.
(2006) studied the emulsification process of a model emulsion from olive oil and phosphatidylcholine, in vitro, and the influence of
polyphenols on this process. It was found that green and black tea polyphenols affected the emulsions by increasing droplet size and
decreasing specific surface area. Phosphatidylcholine possesses hydrophilic heads which face the exterior of the emulsion droplet.
Polyphenols have many hydroxyl groups and may interact with phosphatidylcholine creating complexes. Furthermore, polyphe-
nols may have acted as a linker between complexes to form complex aggregates, thus increasing droplet size.

Interaction With Food Carbohydrates

Food is also usually rich in carbohydrates and the interaction of some of these compounds with polyphenols is well reported. The
first ideas that some polyphenols interact with carbohydrates arise to explain fruit ripening process and subsequent loss of astrin-
gency. This interaction has also been the justification to explain the decrease of anthocyanins extracted during red wine making
process.
 Polyphenol Interactions and Food Organoleptic Properties 3

Fruit ripening process includes several physicochemical and sensory changes, namely texture changes where fruits become soften
and smooth, with reduction of astringency and bitterness (Prasanna et al., 2007). A typical example of these changes is persimmon.
One hundred years ago, Lloyd and co-workers (Lloyd, 1911) suggested that the decrease in persimmon astringency was related to
the loss of tannins’ solubility due to their interaction with carbohydrates presented in tannin-rich cells. Recent evidence revealed
that during grape ripening, tannins bind to cell wall carbohydrates (Braidot et al., 2008). Texture changes during fruit ripening result
from the enzymatic degradation of structural carbohydrates of cells wall, namely pectins, hemicellulose and cellulose, and also
storage carbohydrates (Prasanna et al., 2007), causing the release of small soluble fragments of carbohydrates. So, another
hypothesis for reducing astringent sensation is that these small, soluble fragments would be able to inhibit the interaction of tannins
with salivary proteins (Luck et al., 1994) via two mechanisms (Luck et al., 1994; Ozawa et al., 1987; Mateus et al., 2004) (Fig. 2):
(i) carbohydrates form ternary complex protein polyphenol carbohydrates, which increase solubility in an aqueous medium;
(ii) molecular association occurs in solution between carbohydrates and polyphenols hence competing for salivary protein
aggregation.
Polydextrose (Ares et al., 2009) and carboxymethylcellulose (Troszynska et al., 2010; Smith et al., 1996) can be used to reduce
the astringent properties of aqueous tannin solutions and polyphenol-rich plant extracts. Arabic, guar and xanthan gums also
demonstrated a significant capability to reduce astringent sensation (Troszynska et al., 2010). In general, pectins are the most
effective carbohydrates in restraining the interaction between tannins and proteins (Le Bourvellec et al., 2005; de Freitas et al.,
2003; Soares et al., 2012), and their high affinities to tannins resulting from their ability to develop a gel-like network and form
hydrophobic pockets to encapsulate procyanidins (Le Bourvellec et al., 2005). Whereas, filamentous and globular polysaccharides,
like cellulose and xyloglucan, would bind procyanidins weakly. Another common trait is that acidic carbohydrates seem to have
a more significant effect on decreasing astringency than neutral carbohydrates from the same origin (Vidal et al., 2004). Besides
influencing astringency perception, the tannin-carbohydrate interaction also affects the physical properties of carbohydrates e.g.
the interaction between amylopectin and tea polyphenols favours gelatinization by decreasing the gelatinization temperature
and enthalpy of starch (which is possibly related to easier hydration of starch granules).
Besides tannins, anthocyanins were found to interact with carbohydrates. During wine making, the extent and yield of antho-
cyanin extraction depend not only on their concentration but also the carbohydrate composition of grape cell wall (Busse-Valverde
et al., 2011). In fact, Romero-Cascales and co-workers found that the anthocyanin concentration in the grapes is not directly
correlated with the final concentration in the resulting red wine and the barrier effect of carbohydrates polymers is likely the reason
(Romero-Cascales et al., 2005; Ortega-Regules et al., 2006). Several studies with model carbohydrates (e.g. cellulose and cellulose-
pectin mixtures) or those isolated from grape cells walls have shown their high affinity to anthocyanins and their effect on antho-
cyanins extraction (Padayachee et al., 2012). In general, acylated anthocyanins have greater affinity to carbohydrates than
non-acylated forms. The physicochemical characteristics of carbohydrates, namely porosity, monosaccharide composition and
hydrophobicity affect their interaction with anthocyanins. Differences in the galactose and arabinose contents along with variations
in the cellulose and pectin esterification degree (the lower esterification, the greater interaction) affect the interaction with antho-
cyanins (Ortega-Regules et al., 2006; Buchweitz et al., 2013; Kopjar et al., 2009). Further, anthocyanins occur in different forms with
different hue and intensity in colour (otherwise, colourless) at different pHs. In nature, copigmentation interactions can occur
which promotes the stability of the flavylium form of anthocyanins and associated colour of anthocyanin-rich foodstuffs. Interac-
tion between anthocyanins and pure carbohydrates (e.g. pectins, arabic gum or b-cyclodextrin) have been examined mostly on the
pectin copigmentation effect i.e. a slight stability enhancement of anthocyanins colour (Chung et al., 2016; Howard et al., 2013).
This effect was mostly ascribed to the intermolecular association between the carbohydrate and anthocyanins mainly through
hydrogen bonds and hydrophobic interactions (Fig. 3) (Fernandes et al., 2014).
In summary, the studies discussed here showed that different polyphenols could bind to different food carbohydrates. Depend-
ing on the compounds these interactions could have positive and negative effects. The interaction of tannins with food carbohy-
drates can lead to an astringency and bitterness modulation while anthocyanins interaction with carbohydrates could lead for,

Figure 2 Possible mechanisms to explain the effect of carbohydrates on restraining the formation of tannin/protein aggregates (Mateus et al.,
2004).
4 Polyphenol Interactions and Food Organoleptic Properties

Hydrophobic
interactions

Hydrogen bonds

Anthocyanin self-association
Figure 3 Schematic representation of some interactions established between anthocyanins and a low methoxylated pectin model involving hydro-
phobic interaction and H bonding. Pectin molecule is depicted with sticks coloured in dark grey (Fernandes et al., 2014).

on one hand, to a lower extraction yield, and therefore lower colour intensity on the final product, and on the other hand to stabi-
lization and enhancement of anthocyanins colour.

Interaction With Proteins

Food Proteins
Plant phenolic compounds are known to interact with proteins producing changes in the food (e.g. biological value (BV), colour,
taste).
Polyphenols are known to interact with proteins causing changes in food, e.g. biological value, colour and taste. In some foods,
proteins and polyphenols can form soluble complexes with sizes similar to colloidal particles, causing turbidity of beverages and
limited shelf life. In beer, wine and juice production, polyphenols may induce the development of protein precipitates causing
undesired sensory properties in consumers’ perception (Siebert, 1999; Siebert et al., 1996). Most of the studies on the interaction
of polyphenols with food proteins examined milk proteins, soy proteins, myoglobin (meat protein), lysozyme (egg-white protein)
and gelatin. Beside noncovalent interactions like p–p bonding (aromatic interaction), hydrogen bonding, hydrophobic or ionic
interactions (Siebert, 1999; Siebert et al., 1996), it has been assumed that covalent bonding is likely to play an important role
in protein-polyphenol interactions (Rawel et al., 2001; Beart et al., 1985).
Beside noncovalent interactions like p–p-bonding (aromatic interaction), hydrogen bonding, hydro-phobic or ionic interactions
(Valavanidis and Vlachogianni, 2013; Scalbert and Williamson, 2000), it has been assumed that covalent bonding is likely to play
an important role in protein–phenol interactions.
Polyphenols, in general, interact with globular proteins and can cause structural and conformational changes in proteins.
Interaction of milk proteins with tea polyphenols induces structural changes in both whey proteins and (a- and b-) caseins (Hasni
et al., 2011; Kanakis et al., 2011). This interaction leads to reduced protein digestibility and altered antioxidant activity although no
change in polyphenol structure (Stojadinovic et al., 2013; Xiao et al., 2011), as well as reduced tea astringency. An extensive study on
the interactions of fifty-five dietary polyphenols with milk proteins revealed that the binding was strongly influenced by the
structural features of polyphenols (Xiao et al., 2011). Methylation and methoxylation as well as glycosylation of flavonoids
decreased the affinities to milk proteins. Hydroxylation on the rings A and B of flavones and flavonols enhanced slightly the inter-
action, whilst hydroxylation on the ring A of flavanones significantly improved the affinities. Galloylation of catechins significantly
increased the affinity by 100–1000-fold. Glycosylation of resveratrol decreased its affinity for milk protein. Esterification of gallic
acid increased its binding affinity. Soy proteins, especially soy glycinin and soy trypsin inhibitor, were shown to react with several
phenolic acids (gallic, chlorogenic and caffeic acids), flavones (flavone and apigenin) and flavonols (kaempferol, quercetin and
myricetin) giving protein derivatives. The secondary and tertiary structure of the proteins is changed as a result of these interactions,
influencing their surface properties and making them hydrophilic in nature (Rawel et al., 2002). In the same way, myoglobin also
suffers structural changes upon interaction with o-, and p-hydroxyphenols, p-quinone and gallic acids (Kroll and Rawel, 2001),
causing lower digestion by tryptic, a-chymotryptic, peptic and pancreatic proteases. Lysozyme is also modified upon its covalent
attachment to certain phenolic compounds (m-, o-, p-dihydroxybenzenes, ferulic and gallic acid) (Rawel et al., 2001). The deriva-
tization was accompanied by the reduction of solubility over a broad pH range and increase of hydrophobicity, with the isoelectric
points shifted to lower pH values and high molecular weight fractions formed. Furthermore, the peptic digestion of the derivatized
lysozyme was adversely affected, whereas the tryptic, chymotryptic and pancreatic hydrolysis seemed in favour.
 Polyphenol Interactions and Food Organoleptic Properties 5

Besides modifications on the biological value of these proteins due to reduced digestibility, changes in protein hydrophilic/
hydrophobic properties are induced by the interaction with polyphenols causing altered protein solubility and different functional
and sensory properties of food (e.g. emulsion- and foaming properties, gel building, etc.) (Rohn et al., 2006). Strong interactions
occur between polyphenols and proteins with flexible and open structures (usually with a high proline content, e.g. gelatin) (Asano
et al., 1982; Oh et al., 1980; Hagerman and Butler, 1981; Frazier et al., 2010). Gelatin is a mixture of polypeptides derived from
collagen and often used as wine fining agent. In fact, fresh wine is a turbid, complex and physicochemically unstable hydroalcoholic
solution. Its limpidity, which is highly appreciated and required by consumers, is achieved through several processes like natural
sedimentation, filtration and centrifugation. Still, a limpid wine has to remain that way during the period of bottle ageing and
storage. In white wine production, chemical oxidation of catechins and proanthocyanidins is the main source of browning, affecting
the colour, aroma and taste of white wine (Spagna et al., 2000). Accordingly, clarification and stabilization of wines are mainly
achieved through addition of proteins, a process known as “fining.” Protein components in gelatin bind to wine polyphenols to
form complexes which would precipitate out of solution and thereby potential browning is minimized (Spagna et al., 2000;
Sarni-Manchado et al., 1999). Maury et al. (2001) characterized the fining abilities of a commercial gelatin (average molecular
weight 25,000 Da) and gelatin fractions (16,000–190,000 Da) for tannin removal. Selective precipitation occurred between gelatin
and highly polymerized or galloylated tannins, and more polymerized tannins was precipitated by the 16,000 Da gelatin than by
the 190,000 Da gelatin. In addition, the gelatin-treated wines were significantly less astringent than the unfined wine. Another study
also reported the significant differences caused by various hydrolysed gelatins in wine chemical composition and polyphenol
profile, and a preference for the treated wines over untreated ones (Karamanidou et al., 2011).
It has been shown that the protein-polyphenol binding increases with the molecular size of the polyphenol molecule (de Freitas
and Mateus, 2001) and is affected by polyphenol conformational flexibility (Haslam et al., 1992). The above-mentioned studies
indicate that some structural features of polyphenol molecules are important for this kind of interaction: (i) molecular weight,
(ii) structural flexibility and (iii) number of OH groups.

Salivary Proteins
The most recognized mechanism for astringency perception involves the interaction between tannins and salivary proteins. In 1954
Bate-Smith (Bate-Smith, 1954) proposed that astringency results from the interaction of tannins with salivary proteins in the oral
cavity, mainly proline-rich proteins (PRPs), and since this idea has been generally accepted and supported by numerous studies in
the literature (Sun et al., 2013; Rinaldi et al., 2012; Kallithraka et al., 1998; Bennick, 2002; Mehansho et al., 1987; Soares et al.,
2011). Moreover, some studies reported the differences in reactivity of several families of salivary proteins. HPLC and SDS-
PAGE analyses demonstrated that when all the major families of salivary proteins were presented in a competitive assay, which
simulated the oral cavity, condensed tannins interacted firstly with acidic PRPs and statherin, then with histatins, glycosylated
PRPs and finally basic PRPs (Soares et al., 2011). It seems that in vivo astringency intensity and development with time may be
related to the modifications of different salivary proteins. In the case of a low concentration of tannins for the first exposure to
PRPs, the precipitation of acidic PRPs and statherin correlated with the intensity of astringency. However, for higher concentrations
of tannins upon subsequent exposures, the relative astringency likely correlated to gPRPs precipitation. These results were reported
for the first time that the several families of salivary proteins could be involved in different stages of astringency development
(Soares et al., 2011; Brandão et al., 2014).
In summary, polyphenol–protein interactions might potentially influence the availability of certain amino acids and protein
structure, which could affect the functionality and digestibility of proteins. However, the extent of this influence depends on the
origin and nutritional quality of proteins, and food processing conditions and other co-existing food nutrients. Furthermore, poly-
phenols bind to salivary proteins inducing the perception of astringency in the oral cavity, whilst the binding of polyphenols to
some other (food) proteins can modulate this perception. So, at the end, interaction of polyphenols with proteins, as one of the
most important interactions, is very complex with many positive and negative effects thus its characterization requires many
different areas of knowledge.

Concluding Remarks

Studies discussed here show that polyphenols are able to interact with other food compounds. The referred interactions have many
side effects on sensory properties. Most of the current discussion focused on colour and taste. Also, the effects of these interactions,
positive or negative, depend on the end use. Although polyphenol–lipid interactions have scarce data, it seems that this interaction
can affect lipid emulsion properties; Polyphenol-carbohydrate interactions can lead to an astringency and bitterness modulation as
well as affect anthocyanin colour; Polyphenol-protein interactions can affect astringency and also affect some functionalities of
proteins in food. Literature review revealed that most studies on these interactions are only focused on the bioavailability of the
involved compounds. More studies are needed to investigate other sensory properties that could be influenced by these interactions
such as food texture and pleasantness, especially in relation to the interaction with food lipids.
6 Polyphenol Interactions and Food Organoleptic Properties

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