WO2013023942A1 - Food compositions comprising flavan-3-ols - Google Patents

Abstract

Disclosed are food compositions comprising certain compounds and flavan-3-ols such as catechins and other tea-derived flavan-3-ols. Also disclosed are methods for manufacturing the compositions and use of the compounds for reducing or eliminating an unpleasant taste caused by the flavan-3-ols in food compositions. The compounds are those of formula (I) or a physiologically acceptable salt thereof, wherein M is hydrogen or hydroxyl, preferably hydroxyl, and A is a carbohydrate moiety, preferably an oligosaccharide moiety.

Description

FOOD COMPOSITIONS COMPRISING FLAVAN -3-OLS

TECHNICAL FIELD

The present invention relates to food compositions comprising flavan-3-ols such as catechins and other flavan-3-ols found in tea. In particular the present invention relates to food compositions comprising the flavan-3-ols and certain oleanene-type triterpene glycosides which are capable of reducing or eliminating unpleasant tastes.

BACKGROUND

Tea has recently gained wide attention for its potentially beneficial effects on human health. Several epidemiological, clinical and experimental studies have established a positive correlation between tea consumption and certain health benefits. Taken regularly, tea has been reported to help improve, for example, vascular function, combat fatigue, reduce cholesterol levels and increase feelings of vitality.

The health benefits of tea are primarily attributed to its high flavonoid content. Flavan-3-ols are the major flavonoid compounds in tea and include the catechins found in green tea. Epigallocatechin gallate, epicatechin, epicatechin gallate, and epigallocatechin and their respective stereoisomers or mixtures have been shown to positively impact physiological activities, and their use as antiallergenic agents and cerebral function activators has been proposed. Unfortunately, a higher level or concentration of catechins in a food product can often lead to poor organoleptic properties, in particular to a bitter taste and/or astringent taste.

During the processing of fresh tea leaves in order to obtain so called black tea (sometimes also called red tea) the colourless catechins are converted to coloured flavonoids, including the flavan-

3-ols known as theaflavins and thearubigens. As with catechins, the higher molecular weight theaflavins and thearubigens have a very bitter and astringent taste.

A bitter taste mostly is caused by substances which bind to bitterness receptors on taste cells (which are to be found in the "taste buds" on the tongue) and transmit a signal to the brain via neurochemical cascades, said signal causing a defensive reaction and a negative taste impression (Meyerhof, Rev. Physiol. Biochem. Pharmacol. , 2005,154: 37-72).

An astringent taste is thought to be caused as a rule by precipitation of proline-rich proteins in the saliva by astringent substances. The homogeneous saliva, which normally serves as a "lubricant" in the oral cavity, then contains denatured proteins, which reduce lubricity and thus leave behind a rough or dry feeling in the mouth, which is felt to be astringent (Lesschaeve ef a/., Am. J. Clin. Nut , 2005, 81 : 3308-58) European patent EP 1 297 749 B1 (Kao Corporation) discloses a beverage with a concentrated or purified tea extract incorporated therein. The beverage, which contains catechins in combination with quinic acid at a predetermined ratio, is said to have an improved taste. More specifically, the beverage is said to be free from the unpleasant aftertaste which would otherwise remain after alleviation of the bitterness or astringency peculiar to catechins by a sweetener or the like.

USA patent application published as US 2003/0096050 (Kao Corporation) discloses a food composition containing catechins (i.e. flavan-3-ols) and gallic acid wherein the gallic acid is alleged to have a certain bitterness mitigating effect.

International patent application published as WO 2010/026003 (Unilever) discloses the use of certain compounds for the reduction or elimination of bitterness caused by flavan-3-ols. The compounds include one or more of cinnamic acid, 4-phenylbutanoic acid, 3-(3,4,5- trimethoxyphenyl)propanoic acid, 3,4,5-trimethoxycinnamic acid, 3-(4-methoxyphenyl)propanoic acid, 4-methoxycinnamic acid, 2,4-dimethoxycinnamic acid, 3-(3,4-dimethoxyphenyl)propanoic acid, 3,4-dimethoxycinnamic acid, 4-hydroxycinnamic acid, 3-(3,4-dihydroxyphenyl)propanoic acid, 3,4-dihydroxycinnamic acid, 3-(3-methoxy-4-hydroxyphenyl)propanoic acid, 3-methoxy-4- hydroxycinnamic acid, and 4-hydroxy-3,5-dimethoxycinnamic acid. The substances known to reduce, modulate, mitigate or suppress bitter and/or astringent taste impressions, including other substances not mentioned above, are often limited in their use, for example due to their properties or incompatibility with other ingredients often used in food compositions (e.g. poor solubility in typical diluents, instability, discoloration, unpleasant taste, off- notes or the like). In addition the substances themselves may have strong tastes which may be undesirable or at least limit the degree of freedom a formulator has in designing a food product.

Thus the present inventors have recognised a need to provide further substances (one or more compounds) able to modify or to mask (i.e. reduce or suppress) unpleasant taste impressions, in particular bitter and/or astringent taste impressions in foodstuffs comprising flavan-3-ols. Said substances should preferably be compatible with other ingredients typically used in foods (like solvents, carriers, flavouring substances, sweeteners, antioxidants, vitamins, and the like), in particular preferably be stable and/or be sufficiently soluble in typical diluents. In addition, said substances themselves should preferably not have a strong taste, i.e. have a rather neutral taste profile, and preferably should not impart unpleasant taste impressions, at least not to a significant extent, at the levels said substances are used in the food compositions. Said substances should then for example be compatible with many different aroma or flavour substances and flavour types, preferably without deteriorating or affecting the overall taste impression and taste profile of the respective food composition. The present inventors have found that this need may be met by employing certain compounds having an oleanene-type triterpenoid aglycone moiety with a saccharide chain attached thereto in foodstuffs comprising flavan-3-ols. Specific examples of these compounds include certain saponins.

Saponins are known and occur in a wide variety of plants such as peanuts, lentils, lupins, alfalfa, oats and spinach. Based and depending on their aglycone structure, saponins are generally categorized into three main groups as groups A, B, and E (see Heng, Dissertation, 2005, University of Wageningen, Netherlands). Group B saponins are derivatives of the aglycone sapogenol B (Shiraiwa, Agric. Biol. Chem., 1991 , 55(4): 91 1-7).

The identification and analysis of saponins is also described in the literature, see e.g. Lee ef. al., J. Mass. Spectrom. 1999, 34, 804-812 and Fuzzatti ef. a/., J. Chromatography A, 1997, 777, 233- 238.

Hu ef al. describe in J. Nutr. 2004, 134, 1867-1873 the results of a feeding study conducted to evaluate soy saponin bioavailability in humans. In this study a concentrated soy extract containing a high amount of group B soyasaponin (including soy saponin I and soy saponin II) was used. Philbrick ef al. (Kidney International 2003, 63, 1230-1239) investigated the effect of different soy- derived products comprising soysaponin B_b in a mouse model of polycystic kidney disease.

Saponins are generally known for having a bitter taste (see e.g. JP 2008/173090, JP H04-364130). For example, soy saponin I is described as the bitter principle of the pea (Pisum sativum) in J. Sci. Food. Agric , 1984, 35(8): 887-92). USA patent US 6,426, 1 12 discloses soy products having improved odour and flavour. US 6,426, 1 12 suggests the use of several substances, for example rosemanol or salts of gallic acid, to obtain an odour-reduced soybean product.

DEFINITIONS

The definitions of terms and expressions given in the present text preferably have the general or specific meaning indicated respectively, and in each embodiment one, more than one or all definitions, independently of each other, may be replaced with the more specific definitions, thus defining further more preferred embodiments of the present invention, respectively. As used herein the term "comprising" encompasses the terms "consisting essentially of" and "consisting of". For the avoidance of doubt, the word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of". In other words, the listed steps or options need not be exhaustive. Except in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use may optionally be understood as modified by the word "about". All percentages and ratios mentioned herein are by weight of the composition unless otherwise indicated.

Wherever "%" and percentages are used in the present text, these refer to the weight, i.e. % means % by weight; except where otherwise explicitly defined.

Wherever used in the invention "ppm" is defined as part per million by the weight portion of the part of interest of the total weight, e.g. ppm is meant as ppm by weight; except where otherwise explicitly defined. In the present text, unless indicated otherwise, the terms "solid", "solids", "liquid", "liquids" and the like relate to the state of a substance or substance mixture at 25 °C at 1013 mbar.

It should be noted that in specifying any range of values or amount, any particular upper value or amount can be associated with any particular lower value or amount.

"Obtainable" means that a product (e.g. extract or compound) may be obtained by the specified or other methods, preferably it is obtained by the specified method.

The disclosure of the invention as found herein is to be considered to cover all embodiments as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found with multiple dependency or redundancy.

Flavan-3-ols

As used herein the term "flavan-3-ols" is used as a generic term for catechins, theaflavins, thearubigins, and mixtures thereof.

As used herein the term "catechins" is used as a generic term for catechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, their respective stereoisomers, tautomers, salts, solvates, hydrates, and mixtures thereof (as known from the literature, see e.g. Gu ef a/., J. Nutr., 2004,134,613-7). "Gallated catechins" is used herein as a generic term for catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate and mixtures thereof. "Exogenous catechins" means catechins derived from a source other than tea, for example catechins derived from grape or cocoa or synthetic catechins. As used herein the term "theaflavins" is a generic term for theaflavin, isotheaflavin, neotheaflavin, theaflavin-3-gallate, theaflavin-3'-gallate, theaflavin-3,3'digallate, isotheaflavin-3-gallate, epitheaflavic acid, epitheaflavic acid-3'-galiate, theaflavic acid, theaflavic acid-3'-galiate and mixtures thereof. The structures of these compounds are well known (see Drynan et al., Nat. Prod. Rep. , 2010, 27: 417-462). The term theaflavins includes all stereoisomers, tautomers, salts, solvates or hydrate forms of these compounds. The preferred theaflavins are theaflavin, theaflavin- 3-gallate, theaflavin-3'-gallate, theaflavin-3,3'-digallate and mixtures thereof, as these theaflavins are most abundant in natural sources, such as black tea. Thearubigins are higher molecular weight flavan-3-ols. Analytical methods exist for determining the thearubigin content of tea flavonoids. One such method is given in Christiane Lakenbrink, Svenja Lapczynski, Beate Maiwald, and Ulrich H. Engelhardt. J. Agric. Food Chem. , 2000, 48 (7), 2848- 2852. Tea

As used herein the term "tea" refers to material from the plant Camellia sinensis, especially Camellia sinensis var. sinensis and/or Camellia sinensis var. assamica. The tea may have been subjected to a so-called "fermentation" step wherein the tea catechins are oxidised by certain endogenous enzymes that are released during the early stages of "black tea" manufacture. This oxidation may even be supplemented by the action of exogenous enzymes such as oxidases, laccases and peroxidises. Alternatively the tea may have been partially fermented ("oolong tea") or may have remained substantially unfermented ("green tea").

The term "tea-based beverage" refers to a beverage comprising at least 0.01 wt. % of tea solids. Preferably, a tea-based beverage comprises from 0.04 to 3 wt. % tea solids, more preferably from

0.06 to 2 wt. %, most preferably from 0.1 to 1 wt. %, based on the total weight of the tea-based beverage.

"Leaf tea" for the purposes of this invention means a tea product that contains tea leaves in an uninfused form, and that has been dried to a moisture content of less than 30% by weight, and usually has a water content in the range 1 to 10% by weight (i.e. "made tea").

"Tea concentrate" refers to a tea product comprising greater than 3% by weight of tea solids and preferably from 5 to 99.9% tea solids. The tea concentrate may be a liquid tea concentrate (for example, a tea syrup) or a solid tea concentrate (for example, a tea powder, especially an instant tea powder). Where the tea concentrate is a liquid, it will usually have a moisture content in the range of from 40 to 95% by weight. Where the concentrate is a solid it will typically have a moisture content of less than 30% by weight, more preferably from 1 to 10% by weight.

Compounds "A compound of the formula (I)" or "compound(s) of the formula (I)" and the like as used herein refers to one or more compounds of the formula (I) herein below, that is one compound or a mixture of compounds of the formula (I), or to the use of a compound of the formula (I), where reference to compound(s) of the formula (I) includes the compound(s) as such or in the form of a salt (especially a physiologically acceptable salt), a solvate and/or a tautomer thereof.

This means that either a single compound (preferably in substantially pure form or as a direct extract or a further enriched extract) or a mixture of two or more compounds of the formula (I) (mixtures being preferred, preferably in form of an extract) is used according to the present invention.

This also means that either a single compound (preferably in substantially pure form or as a direct extract or a further enriched extract) or a mixture of two or more compounds of the formula (I) (mixtures being preferred, preferably in form of an extract) is present in or is the ingredient (a) of the present invention.

"Substantially pure form" means that impurities are present only in small or in trace amounts, preferably less than 5 % by weight, more preferably less than 4 % by weight, less than 3 % by weight, less than 2 % by weight, less than 1 % by weight, less than 0.5 % by weight, or less than 0.2 % by weight, most preferably 0.1 to 0.001 % by weight .

Carbohydrate

For the purpose of the invention the term "carbohydrate" and "saccharide" is used in conformity with the lUPAC recommendations (PAC, 1995,67, 1307). These terms particularly refer to mono- or oligosaccharidyl moieties bound via one of their oxygen atoms forming a glycosidic bond. The carbohydrates forming the basis for such moieties include, but are not limited to, uronic acids, monosaccharides, disaccharides, further oligosaccharides. Uronic acid for example are monocarboxylic acids formally derived by oxidation to a carboxy group of the terminal -CH₂OH group of aldoses. Preferably these uronic acids includes, but are not limited to, oxidation products of hexapyranoses, e.g. glycopyranuronic acids such as glucuronic acid, galacturonic acid, iduronic acid, alluronic acid, alturonic acid, mannuronic acid, taluronic acid. Of particular interest are glucuronic acid and galacturonic acid. Monosaccharides for example include, but are not limited to, aldopentoses such as arabinose, lyxose, ribose and xylose, or desoxypentoses such as deoxyribose; and aldohexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose and talose, or desoxyhexoses such as rhamnose, cymarose, fucose, 2-desoxyglucose or 2- deoxygalactose. Disaccharides for example include, but are not limited to, kojibiose, sophorose, nigerose, laminaribiose, maltose, cellobiose, isomaltose, gentiobiose, lactose, melibiose, neohesperidose, rutinose, primeverose, sambubiose, xylobiose, lathyrose and mannobiose.

Salts The term "salt(s)", as employed herein, denotes acidic and/or basic salts formed with inorganic and/or organic acids and bases. In addition, when a compound of the formula (I) contains both a basic moiety and an acidic moiety, "inner salts" may be formed and are included within the term "salt(s)" as used herein. Physiologically acceptable salts (i.e. also being pharmaceutically, nutritionally, nutraceutically and cosmetically acceptable) are preferred, although other salts may also be used, e.g., in isolation or purification steps which may be employed during preparation. Salts of compounds of the formula (I) may be formed, for example, by reacting a compound of the formula (I) with an amount of acid or base, such as an equivalent amount, in a medium such as one in which the salt precipitates or in an aqueous medium followed by lyophilization. Also ion exchangers can be used to form salts from free forms or free forms from salts of a compound of the formula (I). In case of more than one salt-forming group are present up to all of these may form salts even with different types of counterions. "Free form" refers to "form without salt forming counterions", e.g. in non-salt form. Salts of compounds of the formula (I) may be formed in various stoichiometric proportions.

Where the compounds of the formula (I) are mentioned in the present disclosure, this also includes the corresponding (especially physiologically acceptable) salts thereof, also where not explicitly stated. Foods

"Food" in the present text means a raw, cooked, or processed edible substance, ice, beverage, or ingredient used or intended for use or for sale in whole or in part for human consumption, or chewing gum. The term "beverage" refers to a liquid product for drinking, usually including water, which may be consumed to quench thirst, to provide nutrition, for pleasure or relish purposes and/or for other functional purposes (e.g. to administer medicines or other functional materials). Preferably, a beverage comprises at least 85 wt.% of water, more preferably at least 90 wt.% and most preferably from 95 to 99.9 wt.%, based on the total weight of the beverage.

The term "frozen confection" means a sweet-tasting fabricated foodstuff intended for consumption in the frozen state (i.e. under conditions wherein the temperature of the foodstuff is less than 0 °C, and preferably under conditions wherein the foodstuff comprises significant amounts of ice). Frozen confections include ice cream, sorbet, sherbet, frozen yoghurt, water ice, milk ice and the like.

The term "chocolate" means a fat-based foodstuff made primarily of cocoa solids, and typically also containing sugar or other sweeteners, emulsifier and optionally non-fat milk solids. "Chocolate analogue" means a chocolate-like material which contains fats other than cocoa butter, for example coconut oil. Chocolate analogues usually contain non-fat cocoa solids, but it is not essential that they do so. For example, a white chocolate analogue may consist essentially of vegetable oil and sugar, together with colours and / or flavours.

SUMMARY OF THE INVENTION

In a first aspect the present invention provides a food composition comprising:

(a) an ingredient comprising at least one compound of formula (I) or a physiologically acceptable salt thereof,

M is hydrogen or hydroxyl, preferably hydroxyl, and

A is a carbohydrate moiety, preferably an oligosaccharide moiety,

and

(b) a substance comprising flavan-3-ols, wherein the substance is selected from tea solids, exogenous catechins or a mixture thereof.

The compounds of formula (I) structurally may be described as having an oleanene-type triterpenoid aglycone moiety with an saccharide chain attached thereto in the position indicated in formula (I).

Surprisingly the saponin compounds of the formula (I) may mask, i.e. reduce or suppress, unpleasant taste impressions, in particular bitter and/or astringent taste impressions (in the human oral cavity) of prominent bitter components of green tea and, of black tea and/or of foods containing a bitterness causing level of flavan-3-ols, even when used in low concentrations.

As found in our own experiments (see the example 1 herein below), at a level of 100 ppm in a 5 wt. % aqueous sucrose solution soy saponin I showed only faint cardboardy, fatty, dusty and mouth drying taste effects, but no bitterness or astringency. In the same concentration soy saponin II was found to be only very weakly mouth drying. Also in the latter case no bitterness or astringency was observed. Thus, in view of these results and our other similar experiments with compounds of formula (I) it seems that, in contrast to the results reported in J. Sci. Food. Agric, 1984, 35(8): 887-92, that at least certain saponins, in particular those described in more detail herein below - in particular when used in low concentrations - do not necessarily produce bitter taste impressions in the oral cavity.

In a further aspect the present invention provides a method for manufacturing the food composition of the first aspect, the method comprising contacting, preferably mixing, ingredient (a) with substance (b). Conveniently ingredient (a) may be a semifinished product such as a flavour composition and the substance (b) may be a food composition or a precursor therefore.

In a still further aspect of the invention there is provided a use of a compound of formula (I) as defined or a physiologically acceptable salt thereof for reducing or eliminating an unpleasant taste caused by flavan-3-ols in a food composition comprising tea solids, exogenous catechins or a mixture thereof.

In a yet still further aspect the present invention provides a method for modulating or masking an unpleasant taste of a food composition comprising flavan-3-ols derived from tea and/or exogenous catechins, the method comprising compounding the food composition with an effective amount of one or more compounds formula (I) or a physiologically acceptable salt thereof.

DETAILED DESCRIPTION

The compounds for use in the various aspects of the present invention conform to formula (I) herein above.

The compounds of formula (I) include all stereoisomers, such as those which may exist due to asymmetric carbons on the various substituents, including enantiomeric forms and diastereomeric forms. Individual stereoisomers of the compounds of the formula (I) of the present invention may, for example, be substantially free of other isomers, or may be admixed with one or more other stereoisomers or be in the form of racemates.

To the extent that compounds the formula (I) and salts thereof may exist in their tautomeric form, all such tautomeric forms are contemplated herein as part of the present invention. The compounds of formula (I) comprise the carbohydrate moiety A.

Preferably a compound of formula (I) used according to the present invention or a physiologically acceptable salt thereof, comprises two or more saccharide moieties, wherein each saccharide moiety, independently from the other saccharide moieties, comprises a ring having 4 or 5 carbon atoms, and wherein preferably each carbon atom of said rings is substituted by at least one substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1- C5-carboxyl and C1-C5-alkoxy.

In a preferred embodiment:

at least one saccharide moiety in A comprises a COOH substituent,

and/or

each saccharide moiety of A, independently from the other saccharide moieties comprises a ring having 4 or 5 carbon atoms, wherein each ring carbon atom of said rings is (i) substituted by one hydrogen, and (ii) independently from each other, preferably additionally bound to an oxygen atom or a substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1-C5-carboxyl, and C1-C5-alkoxy.

Preferably A comprises at least two saccharide moieties of the general formula (II)

(ID bound to each other or to the triterpene aglycone moiety of the compound of formula (I) via the oxygen, the dotted line marking the linking bond, wherein each saccharide moiety, independently from each other, comprises a ring having 4 or 5 carbon atoms, and wherein preferably each carbon atom of said rings is substituted by at least one substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1- C5-carboxyl and C1-C5-alkoxy, wherein preferably

-at least one saccharide moiety in A comprises a COOH substituent,

and/or

each saccharide moiety of A, independently from the other saccharide moieties comprises a ring having 4 or 5 carbon atoms, wherein each ring carbon atom of said rings is (i) substituted by one hydrogen, and (ii) independently from each other, preferably additionally bound to an oxygen atom or a substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1-C5-carboxyl, and C1-C5-alkoxy.

For the sake of clarity, when the dotted line marks the bond between the oxygen atom and the triterpene aglycone moiety, said dotted line marks the bond between the oxygen atom and carbon atom number 3 (according to the oleanane nomenclature) of the triterpene aglycone moiety according to the oleanane nomenclature (see below). In a preferred embodiment, A corresponds to the formula

and is bound to the triterpene aglycone moiety via the oxygen, the dotted line marking the linking bond to triterpene aglycone moiety, wherein E is a saccharide moiety consisting of 1 to 4 saccharide moieties having the meaning given above, preferably the preferred meaning as defined above. The carbohydrates may carry one, several or all hydroxyl groups in modified form, e.g. as etherified hydroxyl or preferably esterified hydroxyl, respectively, for example in acetylated form, e.g. per-acetylated form.

In another preferred embodiment the invention, A comprises or consists of 2 to 5 saccharide moieties, preferably of two or three saccharide moieties.

In the case that group A in formula (I) is a disaccharide, trisaccharide or a higher oligosaccharide the bonds between each saccharide moiety may be of various possible types, e.g. preferably in the form of glycosidic connections of the 1→2, 1→3, 1→4 and 1→6 type, particularly preferred are glycosidic connections of the 1→2 type (i.e. 1 ,2-linkages).

More preferably A is a saccharide moiety of formula (Tri)

(Tri)

wherein preferably the saccharide moiety bound to the triterpene aglycone moiety of the compound of formula (I) via the linking bond marked with the dotted line comprises a COOH substituent and wherein preferably each saccharide ring carbon atom is bound to at least an oxygen atom or a hydroxyl, carboxyl or methyl substituent.

In another preferred embodiment of the present invention A corresponds to formula (TriX)

(Trl-X)

wherein X is hydrogen or -CH₂OH, preferably X is -CH₂OH, wherein A is bound to the triterpene aglycone moiety of the compound of formula (I) via the linking bond marked with the dotted line. In another preferred embodiment of the present invention a compound of formula (III) or a salt thereof is used

(HI)

wherein X is hydrogen or -CH₂OH, preferably X is -CH₂OH.

Most preferably a compound of formula (Ilia)

(lll-a),

or a physiologically acceptable salt thereof is used.

In compounds of formula (I) preferably used in accordance with the present invention the oleanene aglycone has the following absolute stereochemical configuration:

The numbers indicated therein relate to carbon atoms according to the oleanane nomenclature of the lUPAC Recommendations 1999, Revised Section F: Natural Compounds.

Further preferred compounds in the context of the present invention

- 29 -

Particularly preferred compounds of formula (III) used in accordance with the present invention are:

More particularly preferred according to the present invention are the compounds of formula (III) and the physiologically acceptable salts thereof, most particularly soy saponin I [1], azukisaponin V [2], or a mixture thereof.

With compounds of formula (III), and the physiologically acceptable salts thereof, particularly good masking effects were achieved, preferably of bitter and/or astringent taste impressions.

Particularly good masking effects, preferably of bitter and/or astringend taste impressions, were observed when a mixture comprising (i) soy saponin I [1 ] and/or azukisaponin V [2], and (ii) one or more further saponins of formula (I) were used.

Particularly good masking effects, preferably of bitter and/or astringend taste impressions, were also observed when a mixture comprising (i) soy saponin I [1], azukisaponinV [2], and optionally (ii) one or more further saponins of formula (I) were used.

Soy saponin I (CAS number 51330-27-9), also referred to as soyasaponin I, which is a particularly preferred compound of formula (I) of the present invention, may for example be isolated from Medicago sativa L. (alfalfa), Trifolium pratense L. or Trifolium repens L. seed material according the process disclosed in US 4,594,412 (see example 4 thereof) and described therein in detail. Soy saponin II (CAS number 55319-36-3), sometimes also referred to as soyasaponin B_b, which is a particularly preferred compound of formula (I) of the present invention, as such is also known form the prior art. Azukisaponin V (CAS number 82793-05-3), also sometimes called hispidacin, which is a particularly preferred compound of formula (I) of the present invention, may be isolated from Vigna angularis (azuki bean) or Astragalus danicus or Medicago hispida seed material by using the procedure described by Mahato ef a/., Phytochemistry, 1991 , 30: 3389-3393; Pelizzoni ef a/., Gazz. Chim. Ital., 1996, 126: 657-661.

The compound(s) of the formula (I) can e.g. be isolated or the extracts prepared as described in the appended examples. The method for detection can comprise high pressure liquid chromatography (HPLC) or on reversed phase silica gel (C18) with water/acetonitrile-gradient as an elution solvent with UV as well as MS detection which are used for the product analysis and production optimization. It will be clear to those having ordinary skill in this art that the compound(s) of the formula (I), though per se natural products, can alternatively be synthesized according to standard methods leading to compounds identical with the natural compounds, where appropriate methods, for example, can be deduced from the following publications: "March's Advanced Organic Chemistry: Reaction, Mechanisms and Structure", 5th ed. by Michael B. Smith, Jerry March, Wiley-lnterscience; 2001 ; "Classics in Total Synthesis: Targets, Strategies, Methods" by Nicolaou, Sorensen, John Wiley & Son Ltd, 1996 and "The Art and Science of Total Synthesis at the Dawn of the Twenty-First Century" by Nicolaou ef a/., Angew. Chem. Int. Ed. Engl, 2000, 39 (1 ): 44-122. Preferably, the compounds of the formula (I) are natural compounds, that is, compounds that are present in and can be isolated or extracted from natural sources (especially those mentioned in detail above and below) without chemical synthesis steps (though they may also be prepared or modified by chemical synthesis, e.g. acylated or the like) and are thus present as extracts or purified components of extracts, and not derivatives only obtainable by chemical synthesis.

For example, the extraction or isolation and (partial or complete) purification of the compound(s) of the formula (I) can be conducted by removing the cellular parts of the plant material (e.g. by centrifugation and/or filtration) and removing the supernatant, extracting the obtained cellular material as described above or in the examples to obtain an extract (which can already be used in the various embodiments of the invention) and, if desired, further purifying the compound(s) of the formula (I), e.g. by solvent partition or chromatography, to yield the enriched or pure compounds.

Preferably, the total weight of all compounds of formula (I) in an extract (direct or further enriched) is in the range from 0.01 to 99 % by weight, more preferably from 1 to 99 % by weight, in another embodiment from 5 to 99 % by weight, or from 20 to 95 % by weight, or e.g. from 50 to 90 % by weight.

By the term "extract", either a direct extract (in liquid or preferably in dried form), e.g. obtained as described below, or preferably a further enriched extract (obtainable e.g. by one or more further purification steps after extraction, e.g. chromatography, for example as described below) containing one or more, preferably two or more compounds of the formula (I) is meant.

Extraction preferably is carried out with a non polar or weakly polar solvent or solvent mixture, i.e. a solvent or solvent mixture being less polar than water; the preferred obtainable or obtained extracts according to the invention are lipophilic extracts.

Examples of appropriate solvents are organic solvents (two or more of which can also be mixed), e.g. a ketone or an ester, such as acetone and/or ethyl acetate, an ether, e.g. a cyclic ether such as dioxane, and/or (also in a specific embodiment) an alcohol e.g. ethanol, and/or a liquid or superfluid gas, especially supercritical carbon dioxide.

The pH value of the solvents can be modified by adding acids, citric acid, malic acid, maleic acid, succinic acid, fumaric acid, acetic and formic acid or ammonium acetate, respectively.

Preferably, the solvent may be removed after extraction, e.g. by evaporation or precipitation (e.g. by the addition of water).

Preferably, the extracts can subsequently be further enriched by one or more additional purification steps, such as distribution, e.g. between an aqueous and an ether or ester (e.g. diethyl ether or ethyl acetate) phase for one or more times, precipitation (e.g. crystallisation) or especially chromatography, e.g. by HPLC or MPLC, by which it is possible to obtain further enriched extracts or isolated compounds of the formula (I). It is also possible to use other chromatographic methods such as gel permeation chromatography, countercurrent chromatography, or high speed counter current chromatography instead of the absorption chromatography described above.

Subsequent purification by preparative phase HPLC can also be carried out by the person skilled in the art using other stationary phases, such as RP8, phenyl, DIOI, C2, C4, C8 or amino.

The mobile phase mixtures may also contain additional other acids (for example formic acid) or additional buffers (for example ammonium acetate). Preferably, the compound or compounds, in the embodiments of the invention, are enriched in the mixtures or extract or purified extracts, or in another embodiment as single compound, to a percentage, in independent embodiments of the invention, of up to 10, 20, 30, 40, 50, 60, 70, 75, 80, 85, 90, 92, 94, 95, 96, 97 or 98 % or 98-100 % by weight of the complete extract or purified extract, respectively.

The total amount of compounds of the formula (I) and physiologically acceptable salts thereof in a direct extract or a further enriched extract preferably is 5 wt. % or higher, more preferably is 10 wt. % or higher, most preferably is 20-100 wt. %, based on the total weight of the dry mass of the extract.

In another embodiment of the invention, the compounds of the formula (I), a physiologically acceptable salt thereof, and/or an ester thereof, is added in the form of an extract from a natural source or obtained from such an extract. Preferably, the source of the extract is a plant or a plant part from an appropriate plant of the family of Fabaceae.

More preferably the plant is selected from the Genera cited in US 4,594,412 and/or Abrus spec, Albizia spec, Ardisia spec, Astralagus spec, Grotalaria spec, Glycine spec, G/ycyrrhiza spec, Gueldenstaedtia spec, Lathyrus spec, Lupinus spec, Medicago spec, Melilotus spec, Miletlia spec, Phaseolus spec, Pisum spec, Pueraria spec, Robinia spec, Serjana spec, Sophora spec, Sparlium spec, Trifolium spec, Vicia spec, Vigna spec, Wisteria spec; more preferable the plant is selected from the group consisting of Medicago spec, Phaseolus spec, Pisum spec, Trifolium spec, Vigna spec, and Vicia spec; most preferable the Genus is Glycine spec, Trifolium spec, and Vigna spec, in particular the Genus is Trifolium. In another embodiment the species are selected from the group consisting of T. aitonii Rydb, T. amphianthum Torr. & A. Gray, T. andersonii A. Gray, T. andinurn Nutt., T. anemophilum Greene, T. anoden Greene, T. arcuatum, T. arizonicum Greene, T. arvense L, T. attenuatum Greene, T. barbigerum Torr., T. beckwithii Brewer ex S. Watson, T. bicephalum Elmer, T. bifidum A. Gray, T. brandegei S. Watson, T. calocephalum Nutt., T. cassium Boiss., T. caurinum Piper, T. columbianum Greene, T. confusum Rydb., T. dasyphyllum Torr. & A. Gray, T. decodon Greene, T. dichroanthum Boiss., T. elmeri Greene, T. eriocephalum Nutt., T. filipes Greene, T. fragiferum L, T. fucatum Lindt., T. glomeratum, T. gracilentum Torr. & A. Gray, T. guianense Aubl., T. gymnocarpon Nutt., T. hanseni Greene, T. haydenii Porter, T. helleri P. B. Kenn., T. hervieri Freyn, T. heterodon, T. hexanthum Greene, T. hybridum L, T. inaequale Rydb., T. jokerstii Vincent & R. Morgan, T. lacerum Greene, T. laciniatum Greene, T. leibergii A. Nelson & J. F. Macbride, T. lemmonii S. Watson, T. lilacinum Rydb., T. lividum Rydb., T. longipes Nutt., T. macilentum Greene, T. montanense Rydb., T. mullicaule M. E. Jones, T. multipedunculatum Kenn., T. nanum Torr., T. nemorale Greene, T. neurophyllum Greene, T. olivaceum Greene, T. oreganum Howell, T. owyheense Gilkey, T. oxyodon Greene ex Rydb., T. palmeri S. Watson, T. parryi A. Gray, T. pauciflorum Nutt., T. pedunculatum Rydb., T. petrophilum A. Heller, T. piliferum Boiss., T. pinetorum Greene, T. plumosum, T. ponticum Albov, T. pratense L, T. pseudo-albopurpureum P. B. Kenn., T. repens L, T. rivulare Boiss., T. rusbyi Greene, T. rydbergii Greene, T. salictorum Greene ex Rydb., T. saxicolum Small, T. scariosum A. Nelson, T. sclerorrhizon Boiss., T. shastense House, T. spinulosum, T. splendens A. Heller, T. stenolobum Rydb., T. stenophyllum Boiss., T. stoloniferum Muhl. ex A. A. Eaton, T. subcaulescens A. Gray, T. thompsonii Morton, T. trichocalyx A. Heller, T. tricuspidatum Bertero ex Steud., T. tridentatum Lindl., T. uintense Rydb., T. variegatum Nutt., T. villiferum House, T. virginicum Small, T. wormskjoldii Lehm. In particular the species is Trifolium repens. Conventionally, the dried plant parts (for example fresh or dried roots, fruits, seeds, bark, wood, stalks, leaves or blossom [parts]), preferably in comminuted form, are extracted with a solvent suitable for foodstuffs and products consumed for pleasure at temperatures of from 0 °C or from the melting point, respectively to the boiling point of the respective solvent or solvent mixture, then filtered and the filtrate is wholly or partially evaporated, preferably by distillation, freeze drying or spray drying. The resultant raw extract may then be further worked up, for example, treated with acid (for example under pressure), with acidic ion exchangers or with steam, generally at pressures of from 0.01 mbar to 100 bar, preferably at 1 mbar to 20 bar, and/or redissolved in a solvent suitable for foodstuffs. Physiologically acceptable salts of the compounds of formula (I) are preferably those in which the counterion is selected from the group consisting of Na⁺, K⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Al³⁺, Zn²⁺ and combinations thereof.

In particular, non acidic compositions contain the one or more compounds according to formula (I) preferably as a salt, wherein the counterion is preferably selected from the group consisting of Na⁺,

K⁺, NH₄ ⁺, Ca²⁺, Mg²⁺, Al³⁺, Zn²⁺ and combinations thereof.

Where the compounds of the formula (I) are mentioned in the present disclosure, this also includes the corresponding (especially physiologically acceptable) salts thereof, also where not explicitly stated.

The compounds of the formula (I) which contain an acidic moiety (e.g. one or more carboxyl groups) may form salts with a variety of organic and inorganic bases. Exemplary basic salts include ammonium salts, non-toxic metal salts derived from metals of groups la, lb, lla and lib of the Periodic Table of Elements, e.g. alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as calcium or magnesium salts, or salts with other metals, such as zinc, or salts with amino acids such as arginine, ornithine, homoarginine, lysine and the like. Also salts with salt-forming physiologically acceptable carriers are possible and encompassed by the invention. Further, the compounds of the formula (I) may be in the form of their solvates, such as hydrates, of these derivatives.

The compositions of the present invention are food compositions.

Exemplary "food" compositions are bakery products (for example bread, dry biscuits, cakes, other pastry products), confectionery (for example chocolates, chocolate bar products, other bar products, fruit gums, hard and soft caramels, chewing gum), alcoholic or non-alcoholic beverages (for example coffee, tea, wine, beverages containing wine, beer, beverages containing beer, liqueurs, spirits, brandies, fruit-containing carbonated beverages, isotonic beverages, soft drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant beverages (for example instant cocoa beverages, instant tea beverages, instant coffee beverages, instant fruit beverages), meat products (for example ham, fresh or cured sausage preparations, spiced or marinated fresh or cured meat products), eggs or egg products (dried egg, egg white, egg yolk), cereal products (for example breakfast cereals, muesli bars, precooked ready rice products), dairy products (for example milk beverages, buttermilk beverages, milk ice cream, yogurt, kefir, curd cheese, soft cheese, hard cheese, dried milk powder, whey, butter, buttermilk, partially or fully hydrolyzed milk protein-containing products), products made from soy protein or other soybean fractions (for example soy milk and products made therefrom, fruit beverages with soy protein, soy lecithin-containing preparations, fermented products such as tofu or tempe or products made therefrom), fruit preparations (for example jams, fruit ice cream, fruit sauces, fruit fillings), vegetable preparations (for example ketchup, sauces, dried vegetables, deep-frozen vegetables, precooked vegetables, preserved vegetables), snack articles (for example baked or fried potato chips or potato dough products, maize- or peanutbased extrudates), fat- or oil-based products or emulsions thereof (for example mayonnaise, remoulade, dressings, other ready-to-serve meals and soups (for example dried soups, instant soups, precooked soups), spices, seasoning mixtures and in particular powdered seasonings, which are for example used in snack food applications.

More preferably the composition is a spread, dressing, seasoning, bouillon, soup, sauce, frozen food, confectionary, frozen confection, chocolate, chocolate analogue, beverage or beverage precursor.

Particularly preferred are products comprising tea solids and/or cocoa solids as these naturally contain flavan-3-ols. Thus especially preferred are beverages (especially tea-based beverages), beverage precursors (especially leaf teas or tea concentrates), chocolates, chocolate analogues or frozen confections (especially where the frozen confection comprises cocoa solids, chocolate, chocolate analogues or a combination thereof).

The compounds of formula (I) are suitable to modulate, reduce or suppress an unpleasant taste, more preferably a bitter and/or astringent taste, of flavan-3-ols. The flavan-3-ols are usually tea-derived (i.e. employed as part of tea solids) but, in the case of catechins several other food-grade sources are readily available. Thus exogenous catechins may be present and in one embodiment at least part of the flavan-3-ols comprise catechins derived from grape solids, cocoa solids or a mixture thereof.

The most convenient source of catechins, however is tea solids, especially green tea solids, thus it is preferred that where the flavan-3-ols comprise catechins, at least some of the catechins are part of the tea solids.

Gallated catechins are especially prone to imparting bitter and/or astringent tastes to food products. Surprisingly, however we have found that the compounds of formula (I) are capable of modulating or masking bitter or astringent tastes caused by gallated catechins such as epigallocatechin gallate (EGCG). Thus it is preferred that the catechins comprise gallated catechins, more preferably the catechins comprise epigallocatechin gallate.

In addition or as an alternative to catechins, the tea solids (especially black or oolong tea solids) preferably comprise theaflavins, thearubigins or a mixture thereof. The amount of compounds of formula (I) or physiologically acceptable salts thereof, effective for modulating or masking the bitterness and/or astringency of flavan-3-ols has been found to be remarkably low in relation to the amount of flavan-3-ols present in a food composition. Thus the weight ratio of the total amount of compounds of formula (I) in the composition to the total amount of flavan-3-ols in the composition is preferably in the range of 2: 1 to 1 :200, more preferably in the range 1 : 1 to 1 : 100, more preferably still in the range 1 :2 to 1 :70 and most preferably in the range

1 :5 to 1 :50.

The compositions of the present invention may contain amounts of flavan-3-ols of 0.0001 wt% or lower. However the present invention has particular utility in compositions comprising substantial amounts of flavan-3-ols. Thus it is preferred that total amount of flavan-3-ols in the food composition is at least 0.0001 wt%, more preferably at least 0.005 wt%, more preferably still at least 0.01 , even more preferably at least 0.02 wt% and most preferably at least 0.03 wt%. Additionally or alternatively the total amount of flavan-3-ols in the composition is up to 0.4 wt%, more preferably up to 0.2 wt%, more preferably still up to 0.15 wt% and most preferably up to 0.1 wt%.

Where the composition is a precursor for preparing a food or beverage intended for direct consumption, for example where the composition is a beverage precursor such as a leaf tea or tea concentrate, the levels of flavan-3-ols may be considerably higher than those stated above. For example a beverage precursor may comprise flavan-3-ols in a total amount of from 1 to 99 wt%, more preferably from 2 to 50 wt% and most preferably from 5 to 40 wt%.

The total amount of compounds of formula (I) in compositions of the invention can range, for example, from 0.0001-0.1 wt% (= 1 - 1000 ppm), more preferably the total amount is in the range of 0.0005-0.05 wt%, more preferably still in the range of 0.001-0.03 wt%, even more preferably in the range 0.001-0.02 wt% and most preferably in the range 0.0015-0.0125 wt% (= 15 - 125 ppm).

In a preferred embodiment a food composition according to the present invention, preferably in one of the preferred or particularly preferred embodiments, further comprises one or more substances suitable for enhancing the taste impression umami, sweet, salty, spicy, and/or sour.

In a preferred embodiment a composition according to the present invention, preferably in one of the preferred or particularly preferred embodiments, further comprises at least one further substance for modulating or masking an unpleasant taste of flavan-3-ols, preferably in an amount sufficient for modulating or masking an unpleasant taste of an unpleasant substance or substance mixture, wherein preferably the further substance or the further substances are selected from the group consisting of phloretin, homoeriodictyol, eriodictyol, hesperetin, gamma-aminobutyric acid, pellitorine and its isomers, spilanthol, 3',7-dihdroxy-4'-methoxyflavan according to EP 2 253 226 A, phyllodulcin according to EP 2 298 084 A, rubusoside (preferably rubusoside extracts as described in European patent application 1 1 165 566.8), and vanillyllignans (preferably those described in European patent application 1 1 164 373.0).

In a preferred embodiment, a composition according to the present invention, preferably according to a preferred or particularly preferred embodiment as defined above, has a flavour of berries, citrus fruits, pomaceous fruit, spices, herbs, teas and/or mints, preferably selected from the group consisting of peppermint, spearmint, wintergreen, pineapple, acerola, acai, apple, apricot, banana, pear, pomegranate, blackberry, lemon, lime, grapefruit, pomelo, sweet orange, bitter orange, bergamot, mandarin, guava, rose hip, blueberry, raspberry, lingonberry, bayberry, strawberry, elderberry, gooseberry, red currant, black currant, sweet cherry, cherry, kiwi, lychee, mango, melon, plum, papaya, passion fruit, peach, prune, grape, tamarind, cinnamon, nutmeg, vanilla, green tea, black tea, red tea, yellow tea, white tea, oolong tea, rooibos tea, honeybush tea, mate tea, and mixtures thereof. In a most preferred embodiment the food composition is a beverage, more preferably a tea-based beverage.

Preferably, the beverage is transparent. More preferably the beverage has a turbidity of less than 10 NTU (nephelometric turbidity units) as determined according to DIN ISO EN 27027. Even more preferably, the beverage has a turbidity of less than 5 NTU (nephelometric turbidity units), more preferably still of less than 3 NTU, as determined according to DIN ISO EN 27027.

The turbidity is determined in accordance with DIN ISO EN 27027 using scattered light at an angle of 90°. In our own experiments, a LED with 860 nm infrared light was used. The measurements of turbidity may for example be carried out using a laboratory turbidimeter e.g. such as the Hach 2100N IS or NEPHLA turbidimeter from Hach Lange GmbH (Germany).

An especially preferred beverage, more preferably a tea-based beverage, of the present invention comprises one or more sweet tasting substances, preferably selected from the group consisting of the substances of groups (s-1 ), (s-2) and (s-3):

(s-1 ) sweet tasting carbohydrates, preferably sucrose, maltose, fructose, glucose,

(s-2) sugar alcohols, preferably sorbitol, xylitol and/or mannitol,

(s-3) sweeteners, preferably aspartame, neotame, saccharin, sucralose, cyclamate, acesulfame K, stevioside, rebaudioside A, rubusoside, phyllodulcin, glycyrrhizin, glycyrrhetinic acid, and/or the physiologically acceptable salts thereof.

The compounds of formula (I) may be compounded in the compositions of the present invention in substantially pure form, as a direct extract or as a further enriched extract. In addition or alternatively, the compounds in this form may be mixed with auxiliary ingredients prior to contacting with the food composition.

Thus the ingredient (a) comprises at least one compound of formula (I) or a physiologically acceptable salt thereof and preferably consists essentially of, or consists of, the at least one compound of formula (I) or a physiologically acceptable salt thereof.

In a particularly preferred embodiment ingredient (a) is a semifinished product. More preferably a semifinished product comprising:

one or more compounds of formula (I) preferably one or more compounds of formula (III), as defined above, in particular soy saponin I [1], and azukisaponin V [2], and soy saponin II [3], and/or one or more physiologically acceptable salts thereof,

and

one or more carriers selected from the group consisting of maltodextrin, gum Arabic, silica, ethanol. Isopropanol, 1.2-propylene glycol, glycerol, triacetin, and diacetin.

A semifinished product according to the present invention may be in the form of an odouriferous. aroma or flavouring substance composition or a seasoning mixture comprising one or more compounds of formula (I) and at least one, preferably two, three, four, five or more natural or non-natural flavour compounds, preferably at least one, preferably two, three, four, five or more flavour compounds according to the Leffingwell Flavor Base 2010. Natural flavour compounds can be single aroma chemicals prepared by natural methods, or aroma chemical mixtures, extracts, distillates or isolates from naturally occurring or fermented or cooked food or flavouring materials, especially plants, animals, bacteria and fungi allowed commonly as food or flavouring material. In a preferred embodiment these semifinished products can also contain flavan-3-ols in amount sufficient to elicit an unpleasant preferred a bitter and/or astringent taste in the final food prepared by using the semifinished product.

In a preferred embodiment, the semifinished product is a flavour composition, additionally comprising at least one, preferably two, three, four, five, six, seven, eight, nine, ten, or more aroma substances. In a preferred embodiment, the total amount of the compounds of formula (I), preferably of formula (III) as defined above, and/or the physiologically acceptable salts thereof in the semifinished product is in the range of 0.1 - 50 wt%, preferably in the range of 0.25 - 25 wt. %, more preferably in the range of 0.5 -10 wt.%, based on the total weight of semifinished product. Ingredient (a) in the form of a semifinished product is preferably compounded with the food composition preferably in an amount of 0.001 % to 25 wt. %, more preferably in an amount of 0.01 % to 10 wt. %, particularly preferably in an amount of 0.01 % to 2.5 wt. %, based on the total weight of the final food composition. Preferably, a composition and/or a semifinished product according to the present invention is free of phosphatidylcholine.

Preferably, a composition and/or a semifinished product according to the present invention is free of oxidized phosphatidylcholine.

Preferably, a composition and/or a semifinished product according to the present invention does not comprise soy proteins.

A composition and/or a semifinished product according to the present invention preferably is free of oxidized phosphatidylcholine and free of soy proteins.

Preferably, a composition and/or a semifinished product according to the present invention is free of casein. A composition and/or a semifinished product according to the present invention preferably is free of choline chloride.

Preferably, a composition and/or a semifinished product according to the present invention does not comprise unsaturated fatty acids. A composition and/or a semifinished product according to the present invention preferably is free of oxidized phosphatidylcholine, free of soy proteins, free of choline chloride and free of casein.

Preferably, the total amount of fats in a composition and/or in a semifinished product according to the present invention does not exceed 2.2 wt. % (i.e. is from 0-2.2 wt%), based on the total weight of the composition or the semifinished product.

Preferably, the total amount of fatty acid triglycerides with fatty acids having six or more carbon atoms in a composition and/or in a semifinished product according to the present invention does not exceed 2.0 wt.% (i.e. is from 0 to 2.0 wt%), based on the total weight of the composition or the semifinished product.

Preferably, the total amount of proteins in a composition and/or in a semifinished product according to the present invention does not exceed 4 wt. %, preferably is from 0 to 3 wt. %, based on the total weight of the composition or the semifinished product.

In a preferred embodiment, a composition according to the present invention comprises less than 2 wt. % of proteins and less than 2 wt. % of fatty acid triglycerides with fatty acids having six or more carbon atoms, based on the total weight of the composition.

Many substances with bitter and/or astringent taste are significantly stronger and faster perceived from a liquid composition in comparison to a semisolid or solid composition containing the same amount of the same bitter and/or astringent tasting substances. Flavourings (including bitter and/or astringent tasting substances) are released from a liquid composition very early, that is to say essentially immediately upon consumption, in their full strength, and therefore are perceived comparatively as much stronger. This is in particular the case if the semisolid or solid composition contains a higher amount of proteins and/or fats or fatty oils. This is believed to be due to matrix effects. In a preferred embodiment, a composition and/or a semifinished product according to the present invention is a liquid.

A preferred composition and/or a semifinished product according to the present invention at 25 °C and 1013 mbar has a dynamic viscosity of less than 100 mPas, preferably of less than 75 mPas, more preferably of less than 50 mPas, most preferably from 1 to 25 mPas.

Since such liquids generally are liquids with Newtonian flow behaviour, viscosity is independent of the shear rate. The dynamic viscosity is preferably measured with a plate viscometer, preferably according to DIN 53018, e.g. measured with a Brookfield® viscometer.

In another preferred embodiment, a composition and/or a semifinished product according to the present invention is not an oil-in-water emulsion.

In another preferred embodiment, a composition and/or a semifinished product according to the present invention is not a milk or milk product. In another preferred embodiment, a composition and/or a semifinished product according to the present invention is not a soy milk product, preferably not a soybean product.

In another preferred embodiment, a composition and/or a semifinished product according to the present invention is free of soybeans, soy milk, soy yoghurt, tofu and tempeh.

In another preferred embodiment a composition and/or a semifinished product according to the present invention is free of two, three, four, five, six, seven, eight or more, or preferably free of all of the following components: phosphatidylcholine, oxidized phosphatidylcholine, soy proteins, casein, choline chloride, unsaturated fatty acids, soybeans, soy milk, soy yoghurt, tofu and tempeh, and is preferably not an oil-in-water emulsion, not a milk and not a milk product.

EXAMPLES

Example 1 : Example 1.1 : Isolation of a mixture comprising soy saponin I and azukisaponin V from Trifolium repens

Saponin fractions from Trifolium repens were obtained in a method similar to the method described in US 4,594,412. Analysis of a saponin fraction (hereinafter referred to as [Mix B] by H-NMR showed that [Mix B] consisted of soy saponin I (32%), azukisaponin V (50%) and a third saponin of formula (I) of the present invention with M = hydroxyl, i.e. the triterpene aglycone moiety of said saponin corresponded to sapogenol B (18%). These proportions are based on the signal intensities in the NMR spectrum and do not necessarily reflect the proportions by weight. Example 1 .2: Evaluation of taste properties and masking activities

Prior to the experiments regarding the masking activity, the compounds were tested for their taste profiles in a 5 % sucrose solution in water by an expert panel (5-8 skilled persons). Soy saponin I (CAS number 51330-27-9) at 100 ppm showed some faint cardboardy, fatty, dusty and mouth drying effects, soy saponin II (CAS number 55319-36-3) at 100 ppm exhibited a very neutral taste profile and was only very weakly mouth drying. Multiple Time-Intensity Profiling (mTIP) is a descriptive method for sensory evaluation to rate the intensity of different attributes in parallel over a certain period of time. This method combines the advantages of dual-attribute time-intensity (DATI), reducing the number of tests, and of time- intensity profiling (TIP), which allows evaluation of more than two attributes per session. 15 Trained panellists were asked to take two sips of the sample (5 mL). The first sip is to coat the whole mouth with the sample. After the second sip the actual measurement starts and intensities are rated repeatedly after defined time intervals. Multiple attributes can be rated in parallel by using horizontal unstructured line scales for each descriptor. The line scales are presented on the computer screen and the intensities are rated after the first 10 seconds and afterwards repeatedly every 20 seconds over a period of 70 seconds. Data were analyzed by Compusense® five (trademark by Compusense Inc., Guelph, Canada) and represented graphically in a time-intensity curve.

To evaluate the bitterness and astringency masking effects of a 4: 6 (w/w) - mixture consisting of soy saponin I and azukisaponin V (hereinafter referred to as [Mix A], a trained sensory panel was asked to taste and evaluate a test solution comprising 750 ppm epigallocatechin gallate (EGCG) and 125 ppm ascorbic acid according to the method described above. In a next step, the same panel was asked to rate the bitterness and astringency of a test solution containing EGCG and ascorbic acid in the same concentration as described above and, in addition, 20 ppm of [Mix A]. The results of both time intensity curves are compared statistically to determine the reduction of bitterness and astringency after addition of the masking compound. The test was performed twice: The results regarding bitterness and astringency reduction (mean values) are given in the following tables 1 A and 1 B. For calculation of significance, Student's matched pair test was used.

Table 1A: Bitterness reduction after addition of 20 ppm of a mixture of soy saponin I and azukisaponin V [Mix A]

Time (sec) Bitterness without [Mix A] Bitterness with [Mix A] Reduction

0 5.05 4.34 -14%

10 4.22 3.38 -20%

30 3.16 2.12 -33%

50 2.15 1.59 -26%

70 1.59 1.1 1 -30%

Table 1 B Bitterness reduction after addition of 20 ppm of a mixture of soy saponin I and azukisaponin V [Mix A]

Time (sec) Bitterness without [Mix A] Bitterness with [Mix A] Reduction

0 4.89 4.89 0%

10 4.72 4.16 -12%

30 3.68 3.1 1 -15%

50 2.93 2.29 -22%

70 2.07 1.49 -28%

In contrast thereto soyasapogenol B, i.e. the aglycone of soy saponin I and azukisaponin V, did not exhibit any bitter or astringent masking activity.

When using 20 ppm of [Mix B] (as described in example 1.1 ) instead of [Mix A] above, the bitterness and astringency masking effect of was comparable to the masking effect of [Mix A]. When using 40 ppm of soy saponin I [1] alone instead of [Mix A] above, the bitterness and astringency masking effect of was comparable to the masking effect of [Mix A].

When using 20 ppm of soy saponin II [3] alone instead of mixture [Mix A] above, an astringency masking effect was observed Example 2: Semifinished compositions - Flavour compositions

The ingredients - except for 1 ,2-propylene glycol, glycerol and maltodextrin - are mixed in the above-indicated quantity ratios and then either mixed with 1 ,2-propylene glycol and glycerol and completely dissolved therein by gently warming said mixture or mixed with maltodextrin until homogeneous.

Example 3: Spray dried semifinished products for the preparation of a finished food composition

The drinking water is initially introduced into a container and the maltodextrin and gum arabic are dissolved therein. Then soy saponin I [1] and/or azukisaponin V [2] is emulsified into the carrier solution with a Turrax. The temperature of the spray solution should not exceed 30 °C. The mixture is then spray-dried (specified inlet temperature: 185 -195 °C, specified outlet temperature: 70 - 75 °C). The spray-dried semifinished product contains approx. 18 - 22% of the active ingredients soy saponin I [1] and/or azukisaponin V [2]. Example 4: Leaf Tea Compositions

The tea leaves and the semifinished product(s) are mixed and packaged in teabags of filter paper (2 g of composition per bag). For use, 100 - 250 ml of boiling water is poured onto the teabag, which is left to brew for 2 - 5 min.

Example 5: Leaf Tea Compositions

The tea leaves and the semifinished product(s) are mixed and packaged in teabags of filter paper (2 g of composition per bag). For use, 100 - 250 ml of boiling water is poured onto the teabag, which is left to brew for 2 - 5 min. Example 6: Ready-to -Drink Tea Beverage based on Black Tea

Ingredients Amount in wt%

A B

Black tea extract (powder) 1.4 1.4

Water To 100 To 100

Natural peach flavour 0.65 0.65

Sucrose 7 7

Citric acid (crystalline) 1.2 1.2

Ascorbic acid 0.2 0.2

Soy saponin 1 [1], 10 wt.% solution in ethanol 0.05 —

Azukisaponin V [2], 10 wt.% solution in ethanol — 0.1

Example 7: Ready-to -Drink Tea Beverage based on Green Tea, calorie reduced

Ingredients Amount in wt%

A B

Green tea extract (powder) - catechin content 10 wt% 1.4 1.4

Water To 100 To 100

Flavour type lemon 0.65 0.65

Sucrose 3.45 3.45

Saccharin, sodium salt 0.1 —

Rebaudioside A — 0.02

Citric acid (crystalline) 1.2 1.2

Ascorbic acid 0.2 0.2

Soy saponin I [1], 10 wt.% solution in ethanol 0.05 —

Azukisaponin V [2], 10 wt.% solution in ethanol — 0.05

Example 8: Ready-to -Drink Tea Beverage based on Black Tea, sugar free

Example 9: Cappuccino Beverage Mix fortified with Catech

The ingredients are blended. Subsequently, 12.5 g of the final blend are put into 150 ml hot water to prepare the final beverage.

Example 10: Dark Chocolate

A bitter chocolate was prepared from the following ingredients by melting and optionally conching them, pouring the melt into forms and cooling down and tempering the resulting chocolate bars.

Ingredients Amount in wt% A B

Cocoa mass To 100 To 100

Cocoa butter 1 1.70 1 1.70

Sucrose 29.50 29.50

Semi skimmed milk 3.00 3.00

Soy lecithin 0.2 0.2

Vanillin 0.035 0.035

Soy saponin 1 [1], 10 wt.% solution in ethanol — 0.05

Azukisaponin V [2], 10 wt.% solution in ethanol 0.05 0.05

Claims

Claims

1. A food composition comprising:

(a) an ingredient comprising at least one compound of formula (I) or a physiologically acceptable salt thereof,

(l)

wherein

M is hydrogen or hydroxyl, preferably hydroxyl, and

A is a carbohydrate moiety, preferably an oligosaccharide moiety,

and

(b) a substance comprising flavan-3-ols, wherein the substance is selected from tea solids, exogenous catechins or a mixture thereof.

2. The food composition as claimed in claim 1 wherein A comprises at least two saccharide moieties of the general formula (II)

(ID bound to each other or to the triterpene aglycone moiety of the compound of formula (I) via the oxygen, the dotted line marking the linking bond, wherein each saccharide moiety, independently from each other, comprises a ring having 4 or 5 carbon atoms, and wherein preferably each carbon atom of said rings is substituted by at least one substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1-C5-carboxyl and C1-C5-alkoxy. The food composition as claimed in any one of claims 1 or 2 wherein

- at least one saccharide moiety in A comprises a COOH substituent,

and/or

- each saccharide moiety of A, independently from each other, comprises a ring having 4 or 5 carbon atoms, wherein each ring carbon atom of said rings is (i) substituted by one hydrogen, and (ii) independently from each other, preferably additionally bound to an oxygen atom or a substituent selected from the group consisting of hydrogen, hydroxyl, C1-C5-alkyl, C1-C5-OH, C1-C5-carboxyl, and C1-C5-alkoxy.

The food composition as claimed in any one of the preceding claims wherein A comprises or consists of 2 to 5 saccharide moieties, preferably comprises or consists of two or three saccharide moieties, more preferably A is a saccharide moiety of formula (Tri)

(Tri)

wherein preferably the saccharide moiety bound to the triterpene aglycone moiety of the compound of formula (I) via the linking bond marked with the dotted line comprises a COOH substituent and wherein preferably each saccharide ring carbon atom is bound to at least an oxygen atom or a hydroxyl, carboxyl or methyl substituent.

5. The food composition as claimed in any one of the preceding claims wherein A is

(Tri-X) wherein X is hydrogen or -CH₂OH, and

wherein A is bound to the triterpene aglycone moiety of the compound of formula (I) via the linking bond marked with the dotted line.

The food composition as claimed in claim 5 wherein the ingredient (a) is or comprises a compound of formula (III)

wherein X is hydrogen or -CH₂OH.

7. The food composition as claimed in any one of the preceding claims wherein the flavan-3-ols comprise catechins.

8. The food composition as claimed in claim 7 wherein the catechins comprise gallated catechins, preferably epigallocatechin gallate. 9. The food composition as claimed in any one of the preceding claims wherein the flavan-3-ols comprise theaflavins, thearubigins or a mixture thereof.

The food composition as claimed in any one of the preceding claims wherein the weight ratio of the total amount of compounds of formula (I) in the composition to the total amount of flavan-3-ols in the composition is in the range of 2: 1 to 1 :200, preferably in the range 1 : 1 to 1 : 100.

1 1. The food composition as claimed in any one of the preceding claims wherein the total amount of flavan-3-ols in the composition is at least 0.0001 wt%, preferably from 0.005 to 0.4 wt%.

12. The food composition as claimed in any one of the preceding claims wherein the food composition is a spread, dressing, seasoning, bouillon, soup, sauce, frozen food, confectionary, frozen confection, chocolate, chocolate analogue, beverage or beverage precursor.

13. The food composition as claimed in claim 12 wherein the food composition is a beverage or beverage precursor, preferably a tea-based beverage, leaf tea or tea concentrate.

14. A method for manufacturing a food composition as claimed in any one of claims 1 to 13 comprising contacting ingredient (a) with substance (b).

15. Use of a compound of formula (I) as defined in any one of claims 1 to 6 or a physiologically acceptable salt thereof for reducing or eliminating an unpleasant taste caused by flavan-3-ols in a food composition comprising tea solids, exogenous catechins or a mixture thereof.