(12) Patent Application Publication (10) Pub. No.: US 2010/0028444 A1 Matuschek Et Al

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US 201000284.44A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0028444 A1 Matuschek et al. (43) Pub. Date: Feb. 4, 2010

(54) USE OF WATER-DISPERSIBLE (30) Foreign Application Priority Data CAROTENOD NANOPARTICLES AS TASTE MODULATORS, TASTE MODULATORS Feb. 23, 2007 (EP) ...... O7102977.1 CONTAINING WATER-DSPERSIBLE Nov. 26, 2007 (EP) ...... O7121529.7 CAROTENOID NANOPARTICLES, AND, METHOD FORTASTE MODULATION Publication Classification (75) Inventors: Markus Matuschek, Weinheim (51) Int. Cl. (DE); Andreas Ernst, Worms (DE); A6IR 9/14 (2006.01) Christian Köpsel, Weinheim (DE); A2.3L I/236 (2006.01) Martin B. Jager, A2.3L 2/56 (2006.01) Enkenbach-Alsenborn (DE); Alice A2.3L 2/60 (2006.01) Kleber, Bensheim (DE); Michael A2.3L. I./226 (2006.01) Krohn, Lorsch (DE); Holger A63L/655 (2006.01) Zinke, Zwingenberg (DE) A6IP 43/00 (2006.01) (52) U.S. Cl...... 424/489: 426/534: 426/535; 426/537; Correspondence Address: 514/150 CONNOLLY BOVE LODGE & HUTZ, LLP PO BOX 2207 WILMINGTON, DE 19899 (US) (57) ABSTRACT Use of at least one type of water-dispersible carotenoid nano (73) Assignee: BASFSE, LUDWIGSHAFEN (DE) particles as taste modulators in compositions of matter, pro cess for taste modulation of compositions of matter in which (21) Appl. No.: 12/443,266 at least one type of water-dispersible carotenoid nanopar ticles is added to compositions of matter; and also taste modu (22) PCT Filed: Feb. 25, 2008 lators for compositions of matter comprising (86). PCT No.: PCT/EP08/52273 (A) at least one type of water-dispersible carotenoid nanopar ticles and S371 (c)(1), (B) at least one azo compound, comprising at least one azo (2), (4) Date: Mar. 27, 2009 group. US 2010/0028444 A1 Feb. 4, 2010

USE OF WATER-DSPERSIBLE chemically unstable. Because of the favorable properties of CAROTENOD NANOPARTICLES AS TASTE ACK, a higher dosage of this Sweetening agentis sought. This MODULATORS, TASTE MODULATORS higher dosage, however, is only possible with restrictions CONTAINING WATER-DIS PERSIBLE owing to the bitter taste of this Sweetening agent in relatively CAROTENOID NANOPARTICLES, AND, high concentrations. This is because, in particular, the Sweet METHOD FORTASTE MODULATION eners saccharin and ACK have bitter taste attributes, espe cially in high concentrations. FIELD OF THE INVENTION 0008. Many pharmaceutical active compounds, in particu 0001. The present invention relates to the novel use of lar ibuprofen, also have a strongly bitter taste which leads to water-dispersible carotenoid nanoparticles as taste modula reduction in acceptance when the active compound is taken. tors, in particular for reduction of bitter taste and aftertaste in 0009 For reduction of the natural bitter taste, for example compositions of matter, preferably in foods, drinks, articles of tea, coffee or orange juice, these foods and articles con consumed for pleasure, Sweetening agents, animal feeds and sumed for pleasure are either enzymatically treated in order to cosmetics, preferably in foods, drinks, articles consumed for destroy the bitter tasting substances, or the bitter substance is pleasure, Sweetening agents, animal feeds, cosmetics and removed by decaffeination in the case of caffeine in tea and pharmaceuticals which comprise at least one HIS (High coffee. Intensity Sweetener). 0010. A further possibility of modifying the taste impres 0002. In addition, the present invention relates to a novel sion is addition of taste modulators to the desired foods, process for taste modulation, in particular for reduction of drinks, articles consumed for pleasure, animal feeds, Sweet bitter taste and aftertaste of compositions of matter, prefer ening agents, cosmetics and pharmaceuticals. ably foods, drinks, articles consumed for pleasure, Sweeten 0011. It is therefore desirable to find substances which ing agents, animal feeds and cosmetics, preferably foods, Suppress or reduce the unpleasant taste impressions, and also drinks, articles consumed for pleasure, Sweetening agents, can amplify in a targeted manner desired taste impressions. animal feeds, cosmetics and pharmaceuticals which comprise 0012. In particular in the sector of pharmaceutical active at least one HIS (High Intensity Sweetener) in which at least compounds, a great number of Substances which, in particu one type of water-dispersible carotenoid nanoparticles is used lar, modify bitterness, are known. Thus, for example, the as taste modulator. bitter taste of ibuprofen is masked by polylysine and polyargi 0003) Not least, the present invention relates to novel taste nine (cf. international patent application WO 2003/086293), modulators comprising at least one type of water-dispersible by meglumine salt (cf. U.S. Pat. No. 5,028,625), by sodium carotenoid nanoparticles. chloride or sodium-saccharin (cf. international patent appli cation WO 2003/0475550) or by hydroxypropyl-beta-cyclo PRIOR ART dextrin or chewable methacrylic acid copolymers (cf. Modi fying Bitterness, Mechanism, Ingredients And Applications, 0004 Compositions of matter such as foods, drinks, Glenn Roy, 1997) in order to facilitate intake by patients. The articles consumed for pleasure, Sweetening agents, animal bitterness of caffeine may also be reduced by a multiplicity of feeds, cosmetics and pharmaceuticals frequently comprise taste modulators such as, for example, glutamic acid, dical taste Substances which are in principle unwanted or are too cium disalicylate, starch, lactose, manitol and also by phos dominant or too low in the intensity in which they are present. phatidic acid and beta-lactoglobulin (cf. Glenn Roy, 1997) In the sector of Sweeteners, frequently, in addition to the and in addition by hydroxybenzamides, in particular Sweet taste impressions, further taste impressions such as, for hydroxybenzoic acid vanillylamide (cf. Ley et al., Journal of example, a metallic, chemical, bitter or synthetic taste or Agricultural & Food Chemistry, 2006). aftertaste occurs, which adversely affect the overall taste 0013 Further substances which have been used for reduc impression of the composition to be Sweetened. In the context tion of a bitter taste in general and in particular in pharma of the present invention, taste is taken to mean the immediate ceuticals and foods are lecithin, ascorbate and citrate (cf. taste impression which is formed while the composition is Japanese patent application.JP 2001226293), esters of mono situated in the mouth. Aftertaste is taken to mean the taste or diglycerides such as glycerol monostearate and polycar perception after Swallowing, in particular after a waiting time boxylic acids such as Succinic acid (cf. European patent appli of about 30 seconds. cation EP 0732 064 A1), hydroxyflavanones (cf. European 0005 For example, caffeine in tea or coffee, and also hop patent application EP 1258 200A1), 2-phenyl-4-chromanone extracts in beer, are natural bitter substances which, however, derivatives (cf. German patent application DE 101 22898), in too high a concentration cause an adverse taste impression. Sodium sulfate hydrate (cf. Japanese patent application JP In special bitter drinks such as, for example, tonic water or 02025428). In addition, U.S. Pat. No. 5,637,618 discloses the bitter lemon, a characteristic bitter taste caused by the addi use of benzoic acid derivatives for reduction of the bitter taste tive quinine is desired to a particular extent. in drinks and also of Sweetening agents and of potassium 0006 Fruit juices, in particular orange juice, suffer from chloride. The bitter taste of potassium chloride is also inhib impairment of the taste by, e.g., flavonoid glycosides, which ited using 2,4-dihydroxybenzoic acid, carrageenan and thau have a bitter taste. matin (cf. Glenn Roy, 1997: U.S. Pat. No. 5,637,618 and also 0007 Sugar-free drinks which are admixed with sweeten Japanese patent applications.JP04262758 and JP 07083684). ing agents likewise exhibit adverse taste attributes, interalia a 0014. However, the known taste modulators are not com bitter taste or aftertaste. Mixing of various Sweetening agents pletely satisfactory, in particular when the intention is to use reduces the adversetaste impression and optimizes the favor them for reduction of the bitter taste of compositions of matter able attributes. However, it is not possible to imitate the sugar Such as, for example, foods, drinks, articles consumed for taste completely. In addition, individual Sweetening agents pleasure, Sweetening agents, animal feeds, cosmetics and Such as aspartame (ASP) are, in certain cases, incompatible or pharmaceuticals which comprise at least one HIS, but in US 2010/0028444 A1 Feb. 4, 2010

particular ACK, but in particular of HIS-comprising soft <100 nm (cf. Römpp Online 2007, “Solubilisation” and drinks. In this case their bitterness-reducing activity is fre “Micellen Micelles). Examples of such aqueous solubili quently insufficient. If, for this reason, the concentration of sates are disclosed by European patent applications EP 0800 the known taste modulators is increased in order to achieve 825A1 and EP 0848913 A2. These carotenoid nanoparticles Sufficient activity, unwanted physical and/or chemical inter or their aqueous solubilisates are used for injection purposes actions with the remaining components of the respective for parenteral administration and for coloring foods and phar compositions and/or adverse effects, in particular impairment maceuticals, in particular for coloring drinks which must up to complete distortion of the characteristic taste impres remain visually clear. The use as taste modulators is not sion thereof can occur. described. 0015 Water-dispersible carotenoid nanoparticles, pro 0021. The use of beta-carotene as dye in low-calorie soft cesses for production thereof and use thereof are known per drinks which comprise Sweetening agents such as ASP and S ACK is known. One example of such soft drinks is Coca-Cola 0016 For instance, water-dispersible carotenoid nanopar light Sango (R) having the taste of blood oranges. It is not ticles follow, for example, from European patent application known in what form beta-carotene is added to the soft drink. EP 0832569 A2, the paper by Dieter Horn and Jens Rieger, 0022. The joint use of azo dyes such as Yellow 6 and Red “Organische Nanopartikel in wassriger Phase Theorie, 40 for coloring soft drinks which comprise ACK as HIS is Experiment und Anwendung Organic nanoparticles in likewise known. One example of such a product is Diet Sunk aqueous phase—theory, experiment and application, in ist(R) Orange Soda. It is not known whether the azo dyes used Angewandte Chemie, 2001, volume 113, pages 4460 to 4492. also cause a reduction of the bitter taste and bitter aftertaste of or the textbook by J. C. Bauernfeind, “Carotenoids as Colo ACK. It is still less known whether, by means of the joint use rants and Vitamin A Precursors. Technological and Nutri of azo dyes and carotenoids, a taste-modulating action which tional Applications”, Chapter 2, J. C. Bauernfeind and H. is possibly present may be amplified. Kl?ui, "Carotenoids as Food Color, pages 92 to 95, Aca 0023. In addition, the use of azo dyes such as E 110 and E demic Press, ISBN 0-12-082850-2, 1981. Preferably the 129 together with beta-carotene in the food such as bakery carotenoid nanoparticles are spherical or spheroidal particles products and confectionery and also in instant drink powders which have a particle size <1 um, preferably determined on is also known, howeveralways using a combination of Sweet the basis of electron microscope images. The water-dispers ening agents such as ACK and ASP with Sugar in the case of ible carotenoid nanoparticles are present in formulations or confectionery and instant drink powders and Starches in the Suspensions which additionally comprise additives such as case of bakery products. oils, protective colloids, stabilizers or emulsifiers. In this case 0024. Therefore, the abovedescribed prior art including the carotenoids can be crystalline or amorphous. the products available on the market give no cause or indica 0017. These water-dispersible carotenoid nanoparticles tions as to how the abovedescribed problems could be solved. and the carotenoid-comprising formulations which comprise them can be used as additives for foods, for example baking OBJECT OF THE INVENTION mixes or pudding powders, or as dry powders for producing 0025. Accordingly, the object of the present invention was formulations for food supplementation with vitamins in the to provide Substances which may be used outstandingly as human and animal sectors and also for producing pharmaceu taste modulators, in particular for reduction of bitter taste and tical formulations. Owing to their good cold water dispers bitter aftertaste in compositions of matter, preferably in ibility, they are Suitable, in particular, as food dyes, especially foods, drinks, articles consumed for pleasure, Sweetening for soft drinks. The use of these water-dispersible carotenoid agents, animal feeds, cosmetics and pharmaceuticals, prefer nanoparticles and the carotenoid-comprising formulations ably in foods, drinks, articles consumed for pleasure, Sweet which comprise them, as taste modulators is not described. ening agents, animal feeds, cosmetics and pharmaceuticals 0018 Carotenoid nanoparticles, however, can also be which comprise at least one HIS (High Intensity Sweetener), present in carotenoid-comprising formulations which are in particular ACK. O/W microemulsions (oil-in-water microemulsions; cf. 0026. In this case, these substances, in their novel use as Römpp Online 2007, "Mikroemulsionen Microemul taste modulators, must cause no unwanted physical and/or sions). These O/W microemulsions comprise oil droplets of chemical interactions with the remaining components of the a diameter <1 um, where the carotenoids are dissolved in respective compositions of matter, in particular the foods, molecularly disperse form. The use of these water-dispersible drinks, articles consumed for pleasure, Sweetening agents, carotenoid nanoparticles or the O/W microemulsions which animal feeds, cosmetics and pharmaceuticals. In addition, comprise them as taste modulators is not known. they must not adversely affect the characteristic taste impres 0019. However, carotenoid nanoparticles can also be pro sion thereof, in particular they must not impair it or com duced by milling aqueous Suspensions comprising caro pletely distort it. tenoids, modified starch and a Sugar Such as Sucrose, and 0027. In addition, these substances for the novel use as Subsequent drying, as is described, for example, in German taste modulators must be producible on the basis of sub patent application DE 10 2005030952A1. These carotenoid stances which are known perse, readily obtainable and inex nanoparticles are suitable as additives to food preparations, pensive. for example for coloring foods such as drinks, as means for 0028. Furthermore, the object of the present invention was producing pharmaceutical and cosmetics preparations, and to find a novel process for taste modulation, in particular for also for producing food Supplement formulations, for reduction of bitter taste and bitter aftertaste of compositions example multivitamin formulations in the human and animal of matter, preferably for taste modulation of foods, drinks, sectors. The use as taste modulators is not described. articles consumed for pleasure, Sweetening agents, animal 0020. However, carotenoid nanoparticles can also be used feeds, cosmetics and pharmaceuticals, preferably foods, as aqueous solubilisates in mixed micelles of a micelle size drinks, articles consumed for pleasure, Sweetening agents, US 2010/0028444 A1 Feb. 4, 2010

animal feeds, cosmetics and pharmaceuticals which comprise ticals. In addition, they did not adversely affect the character at least one HIS (High Intensity Sweetener), in particular istic taste impression thereof, in particular did not impair or ACK. completely distort it. 0029. The novel process for taste modulation must have 0039. In addition, the water-dispersible carotenoid nano the effect that the taste modulators used do not cause any particles to be used according to the invention, but in particu unwanted physical and/or chemical interactions with the lar the taste modulators according to the invention, could be remaining components of the respective compositions, in produced in a simple manner based on readily available and particular the foods, drinks, articles consumed for pleasure, inexpensive substances which are known perse. Sweetening agents, animal feeds, cosmetics and pharmaceu 0040. In addition, the process according to the invention ticals, and the characteristic taste impression is not adversely had the effect that the taste modulators used did not cause any affected, in particular is not impaired or completely distorted. unwanted physical and/or chemical interactions with the remaining components of the respective compositions, in SOLUTION ACCORDING TO THE INVENTION particular the foods, drinks, articles consumed for pleasure, Sweetening agents, animal feeds, cosmetics and pharmaceu 0030. Accordingly, the novel use of water-dispersible ticals, and the characteristic taste impression was not carotenoid nanoparticles as taste modulators in compositions adversely affected, in particular was not impaired or even of matter has been found. completely distorted. 0031 Hereinafter this novel use of water-dispersible caro 0041. It was especially surprising that the taste modulation tenoid nanoparticles is termed “use according to the inven of a given composition of matter by the use according to the tion. invention, the process according to the invention and the taste 0032. In addition, the novel process for taste modulation modulators according to the invention was outstandingly of compositions of matter has been found in which at least one reproducible, which, precisely in regard to the production of type of water-dispersible carotenoid nanoparticles is added to mass products such as foods, drinks, articles consumed for the compositions of matter. pleasure, Sweetening agents, animal feeds, cosmetics and 0033 Hereinafter, the novel process for taste modulation pharmaceuticals, is a very particular advantage. of compositions of matter is termed “process according to the invention'. DETAILED DESCRIPTION OF THE INVENTION 0034. Not least, the novel taste modulators have been found for compositions of matter which 0042. For the use according to the invention, the process (A) comprise at least one type of water-dispersible carotenoid according to the invention and the taste modulators according nanoparticles and to the invention, the water-dispersible carotenoid nanopar (B) at least one azo compound comprising at least one azo ticles to be used according to the invention are critical. group. 0043. The carotenoid nanoparticles can have any three 0035. Hereinafter the novel taste modulators for compo dimensional shapes, such as, for example, pyramidal, cubic, sitions of matter are termed "taste modulators according to octahedral, icosahedral, platelet-like, needle-shaped, cylin the invention'. drical, spherical or spheroidal shapes. Preferably, they have a spherical or spheroidal shape. More preferably, the spherical ADVANTAGES OF THE INVENTION shape is in the form of a ball. 0044) The particle size of the carotenoid nanoparticles is 0036. In relation to the prior art, it was surprising, and not less than 1 um, preferably between 10 and 900 nm, more predictable by a person skilled in the art, that the object of the preferably between 20 and 700 nm, particularly preferably present invention could be solved by means of the use accord between 20 to 600 nm, very particularly preferably between ing to the invention, the process according to the invention 20 to 500 nm, and in particular between 20 and 300 nm. and the taste modulators according to the invention. Preferably, the particle size is determined from electron 0037. It was especially surprising that the water-dispers microscope images. ible carotenoid nanoparticles to be used according to the 0045. In this case the spheroidal particles are preferably invention, but in particular the taste modulators according to longitudinally prolate and more preferably here have a length the invention, could be used outstandingly as taste modula of 200 to 300 nm and a thickness 100 to 150 nm. Preferably tors, in particular for reduction of bitter taste and bitter after the median particle size of the carotenoid nanoparticles, taste in compositions of matter, preferably in foods, drinks, determined by quasielastic light scattering, is between 10 and articles consumed for pleasure, Sweetening agents, animal 900 nm, preferably 20 to 700 nm, particularly preferably 20 to feeds agents, cosmetics and pharmaceuticals, preferably in 500 nm, in particular 20 to 300 nm. foods, drinks, articles consumed for pleasure, Sweetening 0046. The essential component of the carotenoid nanopar agents, animal feeds, cosmetics and pharmaceuticals which ticles is at least one, in particular one, carotenoid. “Caro comprise at least one HIS (High Intensity Sweetener), in tenoids' is the collective name for carotenes, a group of particular ACK. highly unsaturated, aliphatic and alicyclic hydrocarbons and 0038. The water-dispersible carotenoid nanoparticles to their manifold modified derivatives. The majority are tetrater be used according to the invention, but in particular the taste penes which are made up of 8 isoprene units. The color of the modulators according to the invention, showed no unwanted carotenoids (yellow to red) is based on their polyene structure physical and/or chemical interactions with the remaining having numerous conjugated double bonds. From the basic components of the respective compositions of matter, in par backbone having 40 carbon atoms are derived not only the ticular the food, drinks, articles consumed for pleasure, Xanthophylls Substituted by hydroxyl or oxo groups, but also Sweetening agents, animal feeds, cosmetics and pharmaceu apo-, nor- or seco-carotenoids which have shortened chains or US 2010/0028444 A1 Feb. 4, 2010

open rings, and retrocarotenoids, wherein the double bonds droplets is <1 um. Preferably, the diameter of the oil droplets are shifted. However, the carotenoids can also possess car is 10 to 900 nm, more preferably 20 to 700 nm, and in boxyl groups. particular 20 to 500 nm. 0047. Examples of suitable carotenoids are alpha-, beta 0055. In the liquid formulations (A2) the carotenoids are and gamma-carotene, lycopene, beta-apo-4-carotenal, beta dissolved in molecularly disperse form in the oil droplets. apo-8-carotenal, beta-apo-12-carotenal, beta-apo-8-caro 0056 Preferably, the liquid formulations (A2) further tenic acid, Zeaxanthin, astaxanthin, violaxanthin, canthaxan comprise at least one additive which stabilizes the O/W thin, citranaxanthin, cryptoxanthin, flavoxanthin, microemulsions, in particular at least one polyol. rhodoxanthin, rubiXanthin, flucoxanthin, mutatoxanthin, 0057 The solid formulations (A3) can be produced, for lutoxanthin, auroxanthin, capsanthin, lutein, crocetin, neuro example, by milling carotenoid particles in an aqueous Sus sporene, echinenone, adonirubin, torulene, torularhodin, pension and Subsequently drying. A Suitable process is bixin, peridinin and peridinol, wherein the carotenoids com described, for example, in German patent application DE 10 prising hydroxyl groups and carboxyl groups can be esteri 2005 030952 A1, page 4, paragraph 0032), to page 5, para fied. In particular, use is made of beta-carotene (provitamin graph 0043. A). 0.058 Preferably, the solid formulations (A3) comprise at 0048. The carotenoids can be present in the carotenoid least one additive. Preferably, in the formulations (A3), the nanoparticles in different states of matter. carotenoid nanoparticles are embedded in a matrix of at least 0049. For instance, the carotenoid nanoparticle can be one additive. Preferably, the carotenoid in the carotenoid Solid. In this case the carotenoids in the carotenoid nanopar nanoparticles in question is crystalline. ticles can be present in crystalline form and/or X-ray amor 0059. The liquid formulations (A4) are aqueous solubili phous form, preferably X-ray amorphous form."X-ray amor sates, wherein the carotenoids are present in mixed micelles phous' means that the crystalline fraction is below 10%. of a micelle size <100 nm (cf. Römpp Online 2007, “Solu Preferably, the carotenoids in this case have a high fraction of bilisation” and “Micellen Micelles). all-trans configuration which is preferably at least 50%, and 0060 Preferably, the liquid formulations (A4) comprise at in particular at least 60%. If the solid carotenoid nanoparticles least one additive, in particular at least one additive which are used in combination with at least one additive, they are stabilizes the mixed micelles, in particular at least one emul preferably embedded in a matrix of this additive. sifier. 0050. In addition, the carotenoids in the carotenoid nano 0061 Examples of suitable liquid formulations (A4) and particles can also be present in the liquid state. This is the processes for their production are disclosed by European case, in particular, when the carotenoids are dissolved in a patent applications EP 0800 825A1, page 2, line 52, to page liquid, preferably nonpolar, medium such as, for example, an 3, line 36, and EP 0848913 A2, page 2, line 42, to page3, line oil, or in the form of solubilized mixed micelles. 58. 0051. The carotenoid nanoparticles can be produced by 0062 Preferably, the at least one additive which is used for means of various processes. production of the liquid or solid formulations (A1) to (A4), in 0052 Preferably these processes result in liquid or solid particular the solid formulations (A1) and the liquid formu formulations comprising carotenoid nanoparticles. Prefer lations (A2), is an additive which is permitted under food law ably, these are the solid formulations (A1) and (A3), in par and/or drugs law. Preferably, the additive is selected from the ticular (A1), and the liquid formulations (A2) and (A4), in group consisting of protective colloids, stabilizers against particular (A2). oxidative breakdown, emulsifiers, oils, plasticizers and com 0053. The solid formulations (A1) can be produced, for positions against caking. example, using the conventional and known precipitation 0063 Examples of suitable protective colloids are gelatin, methods, as are described in European patent application EP fish gelatin, starch, chemically or enzymatically modified 0.832 569 A2, the paper by Dieter Horn and Jens Rieger, starch, dextrins, plant proteins, pectins, gum Arabic, casein, “Organische Nanopartikel in wassriger Phase Theorie, caseinate, polyvinyl alcohol, polyvinylpyrrolidone, methyl Experiment und Anwendung Organic nanoparticles in cellulose, carboxymethylcellulose and alginates (cf. R. A. aqueous phase—theory, experiment and application in Morton, Fat Soluble Vitamins, International Encyclopedia of Angewandte Chemie, 2001, Volume 113, pages 4460-4492, or Food and Nutrition, volume 9, Pergamon Press, 1970, pages the textbook by J. C. Bauernfeind, “Carotenoids as Colorants 128 to 131). Preferably, they are present in the formulations in and Vitamin A Precursors. Technological and Nutritional an amount of based on the formulations, 10 to 80% by Applications”. Chapter 2, J. C. Bauernfeind and H. Klaui, weight. “Carotenoids as Food Color, pages 92 to 95, Academic 0064. Examples of suitable stabilizers are alpha-toco Press, ISBN 0-12-082850-2, 1981. The resultant suspensions pherol, tertiary butylated hydroxytoluene, tertiary butylated of nanoparticles are dried using Suitable processes, for hydroxylanisole, ascorbic acid or ethoxyquin (6-ethoxy-1,2- example by spray drying, and used in the form of powders dihydroxy-2,2,4-trimethylduinoline). (A1). Preferably, the solid formulations (A1) comprise at 0065. Examples of suitable emulsifiers are ascorbyl least one additive. Preferably, in the solid formulations (A1), palmitate, polyglycerol esters offatty acids, Sorbitan esters of the carotenoid nanoparticles are embedded in a matrix of at fatty acids, polypropylene glycol esters of fatty acids and least one additive. Preferably, the carotenoid is present in lecithin. Preferably, they are used in an amount of up to 200% amorphous form in the carotenoid nanoparticles of interest. by weight, preferably 10 to 150% by weight, and in particular 0054 The liquid formulations (A2) are O/W microemul 20 to 80% by weight, in each case based on the carotenoids. sions, i.e. oil-in-water microemulsions (cf. also Römpp 0.066 Examples of suitable oils are sesame oil, corn germ Online 2007, "Mikroemulsionen Microemulsions). The oil, cottonseed oil, soybean oil, peanut oil and also the esters particle size of the disperse phase and the diameter of the oil of medium chain plant fatty acids. Preferably, they are used in US 2010/0028444 A1 Feb. 4, 2010 an amount of up to 500% by weight, preferably 10 to 300% by thaumatin, Stevia, Stevioside and neohesperidin dihydrochal weight, and in particular 20 to 100% by weight, in each case cone, preferably ACK, ASP. Saccharin and Sucralose, particu based on the carotenoids. larly preferably ACK and ASP, in particular ACK. Particu 0067. One example of a suitable polyol is glycerol. larly preferably, ACK is used in drinks. 0068 Examples of suitable plasticizers are sugar and 0078 Preferably, the composition of matter is a low-sugar Sugar alcohols such as Sucrose, glucose, lactose, invert Sugar, composition which comprises less than 10g, preferably less sorbitol, mannitol and glycerol. Preferably, they are present in 1 g, of Sugar per liter or per kg of composition, in particular a the carotenoid nanoparticles in an amount of 20 to 70% by Sugar-free composition. Sugars are taken to mean in the weight, based on the formulations. present case, in particular, but not exclusively, mono- and 0069. One example of a suitable anticalking agent is trical disaccharides. cium phosphate. 0079 Preferably, the composition of matter is a low-car 0070 The carotenoid content of the formulations, in par bohydrate composition which comprises less than 1 g of ticular the abovementioned liquid or solid formulations (A1) carbohydrates per liter or per kg of composition, in particular to (A4), can vary widely and can therefore be very well a carbohydrate-free composition. matched to the requirements of the individual case. Prefer 0080 Advantageously, the composition of matter is a ably, the formulations, based on their total amount, comprise composition having less than 100 kJ, preferably less than 10 0.5 to 30% by weight, preferably 1 to 20% by weight, and in kJ, per liter or per kg of composition. Preferably, the compo particular 5 to 15% by weight, of carotenoids. sition of matteris a low-fat composition which comprises less 0071. In the use according to the invention thereof, the than 1 g offat per liter or per kg of composition, in particular abovementioned carotenoid nanoparticles, preferably the a fat-free composition. carotenoid nanoparticles present in the above described for I0081. The low-sugar, low-carbohydrate and/or low-fat, in mulations (A1) to (A4), in particular (A1) and (A2), serve for particular Sugar-free compositions, are preferably an ACK taste modulation of compositions of matter. In particular they Sweetened composition, in particular an ACK-Sweetened serve for reducing the bitter taste and bitter aftertaste of drink. compositions of matter. I0082 In the context of the use according to the invention 0072 The amount of the carotenoid nanoparticles or for and the process according to the invention, at least one azo mulations thereof, preferably the amount of their formula compound which reduces the bitter taste and aftertaste and tions (A1) to (A4), in particular the amount of their formula has at least one azo group can be further added to the com tions (A1) and (A2), can in this case vary widely and thus very positions of matter, in addition to the carotenoid nanopar well adapted to the requirements of the individual case. ticles. Preferably, at least two, in particular two, azo com 0073 Preferably, they are used in an amount such that in pounds are used. Solid compositions of matter a concentration of carotenoids I0083. The mixture of at least one type of carotenoid nano of 0.1 to 100 ppm, preferably 1 to 50 ppm, and in particular 2 particles and at least one azo compound is a taste modulator to 30 ppm, prevails, in each case based on the total amount of according to the invention. This can be added to the compo a composition of matter. sitions of matter as a finished mixture in the form of an 0074. If the compositions of matter are liquids, they are aqueous dispersion or a powder. Or, the individual compo used in an amount Such that, in the liquid compositions of nents of the taste modulator according to the invention are matter, a concentration of carotenoids of 0.1 to 100 mg/l. added to the compositions of matter simultaneously or Suc preferably 1 to 50 mg/l, and in particular 2 to 30 mg/l, pre cessively. Vails. I0084. The amount of the azo compounds can be varied 0075 Preferably, the compositions of matter are foods, widely and thus very well adapted to the requirements of the drinks, articles consumed for pleasure, Sweetening agents, individual case. Preferably, they are used in an amount of 0.1 animal feeds and cosmetics, preferably in foods, drinks, to 100 ppm, more preferably 0.5 to 50 ppm, and in particular articles consumed for pleasure, Sweetening agents, animal 1 to 20 ppm, in each case based on the total amount of a feeds, cosmetics and pharmaceuticals. The drinks are prefer composition of matter. If the composition of matteris a liquid, ably soft drinks, preferably caffeine-comprising soft drinks, the carotenoid nanoparticles are preferably used in a concen in particular cola drinks. tration of 0.1 to 100 mg/l, more preferably 1 to 50 mg/l, and 0076. The compositions of matter preferably comprise at in particular 2 to 30 mg/l. least one High Intensity Sweetener HIS as Sweetening agent I0085. In this case the weight ratio of carotenoid nanopar or Sweetener. HIS is taken to mean compounds of synthetic or ticles to azo compounds can likewise be varied widely and natural origin which have no physiological calorific value, or very well matched to the requirements of the individual case. negligible calorific value in relation to the Sweetening power Preferably, the weight ratio of carotenoid nanoparticles to azo (non-nutritive Sweeteners) and have a Sweetening power compounds is 10:1 to 1:20, more preferably 5:1 to 1:10, and many times higher than Sucrose. The Sweetening power of a in particular 4:1 to 1:4. compound is given by the dilution at which it tastes just as I0086) If, which is particularly advantageous according to sweet as a sucrose solution (isoSweet solution; 0.1 M=4%), the invention, two azo compounds are used, their weight ratio i.e. a solution of a sweetener which is diluted 500 times has an can be varied widely and very well matched to the require isoSweet taste like a Sucrose solution when the Sweetener has ments of the individual case. Preferably, the weight ratio is a sweetening power of 500. 10:1 to 1:10, more preferably 5:1 to 1:5, and in particular 2:1 0077. Examples of suitable HISs are known from Römpp to 1:2. Online 2007, “Sistoffe” Sweeteners. Preferably, the HIS I0087 Preferably, the azo groups of the azo compounds are are selected from the group consisting of acesulfame-potas linked to aryl groups and/or aryl groups having heteroatoms, sium ACK, aspartame ASP. Saccharin and salts thereof, cycla more preferably aryl groups, in particular phenyl groups and/ mate and salts thereof, aspartame-acesulfame salt, Sucralose, or naphthyl groups. In this case, one or more azo groups can US 2010/0028444 A1 Feb. 4, 2010 be present in one azo compound. These azo groups can be groups, ester groups, ether groups, primary and secondary linked independently of one another to aryl groups and/oraryl amino groups, amide groups, nitrile groups and halogen groups having heteroatoms, preferably aryl groups, in par atoms, preferably Sulfonic acid groups, hydroxyl groups and ticular phenyl groups and naphthyl groups. nitro groups, in particular Sulfonic acid groups and hydroxyl 0088 Preferably, at least one aryl group is at least mono groups. Substituted. In this case one aryl group of an azo group can be 0090 Preferably, the azo compounds are selected from the unsubstituted while the other is polysubstituted. group consisting of the compounds 1 to 112 listed hereinafter. 0089. Examples of suitable substituents are sulfonic acid The azo compound can be ionic or nonionic and can be groups, nitro groups, alkyl groups, carboxyl groups, hydroxyl present in charged or uncharged form.

Na" OS/O O\-0 Na" M V O O

HO N2 N

OESEO

O Na"

O Na" Nsn Y ORS- O N Nins

O-SEO Na" I OESEO o-ji=o -- -- Na O Na O

O x\ O Nat O

HO 22 N

OESEO

O US 2010/0028444 A1 Feb. 4, 2010

-continued

OESEO

Na" No Na" 2 N HO C. /{ O

Na" O

OESEO

OuN SN

OH OY. Nat o21 \, US 2010/0028444 A1 Feb. 4, 2010

-continued

HO O-S N V N OH

( ) HO N V N OH

Ca2 HO O O N 7O s

1O & /9 Na 2

n -S O Na" N 2N 9

OES-O Na"

O US 2010/0028444 A1 Feb. 4, 2010

-continued 11 O C a2+ N OFSFO e N N N n S. N O OH sa C o?"VO

C 12 Ca2+ O O

OESf

15 US 2010/0028444 A1 Feb. 4, 2010 10

-continued 16 O

OESEO C Ca2+

N OH O | N O O

17 O Na" | C

18 US 2010/0028444 A1 Feb. 4, 2010 11

-continued 19

O OH N N OH \ /

O O

22 Na" O On M US 2010/0028444 A1 Feb. 4, 2010 12

-continued 23

HO N2 N

OESEO V O Na"

Na" 24 O

OESEO

2 N CO OH

25 Na"

OESEOf

OH HO

O 2 N N sS. O O O \, 4. \ / No Na" O O Na" 26 O

OESEO

US 2010/0028444 A1 Feb. 4, 2010 14

-continued 31

O O Na"

Na" US 2010/0028444 A1 Feb. 4, 2010 15

-continued

37 O O to-K) es\ -o NN ( )

C US 2010/0028444 A1 Feb. 4, 2010 16

-continued 38

/MNO

Na 39

O O Na" On/ \-O

40 s O=S-O I \eo o2 O I S-O I O N A. N OH

US 2010/0028444 A1 Feb. 4, 2010 19

-continued 49 O O . 2 No. 2 N Br 1n O1sN -N

50 O

O Nins

C N

O Ninn

C N US 2010/0028444 A1 Feb. 4, 2010 20

-continued 53 O Br N--

N Br l N Nu

54 O O No o2 l, No Nns l C N - 1. O

55 O NYO us N o? N N.No O Ninn

Br N r 1. O N." O

56 O Ns US 2010/0028444 A1 Feb. 4, 2010 21

-continued 57 N Šs N O so ul N h N Br

58 NO

O /N N

NS N N s So S N -2 N

59 US 2010/0028444 A1 Feb. 4, 2010 22

-continued 60

62 N

l N N Or

N 63 O

N US 2010/0028444 A1 Feb. 4, 2010 23

-continued 64 O s Br Nno NN l N C n | - N

65 O

S so \ 7N N N N Nt ( NH o?\O

66 O O so h OH N O

67 O

C N so SN

C OH

68 O | N

O N-1N Crs C US 2010/0028444 A1 Feb. 4, 2010 24

-continued 69

HO / r N NSN norN

N so t O

N N

No N O Br HN O Br

71 C 2 N -- N

O NC. or N s |

72 O Nn s

N | l N US 2010/0028444 A1 Feb. 4, 2010 25

-continued 73

76 US 2010/0028444 A1 Feb. 4, 2010 26

-continued 77 C H N O C OCh OH O N OH H O N C O 2 N C O O 2

Ol 12 N NH 2 th NH2 79 C C C N 21 C O NH 2N N HN C O 2 N C C

N N N ( ) NM X N 8 NH K) H 81

1N1- O N

OH Ns O US 2010/0028444 A1 Feb. 4, 2010 27

-continued 82

86 US 2010/0028444 A1 Feb. 4, 2010 28

-continued 87

HN MN ( ) N N s NM K)

88 ()-yr-OOH NR

89 C

h OH O C N N H

90 C

H N h OH O N C C N O OH N N O H C O C US 2010/0028444 A1 Feb. 4, 2010 29

-continued 91

O N

HN O C

O N OH O DOC O NH o1

92 O

OH O

N N H O r

93 O

C o1 H N N OH O

O N N C O C 1.

O h OH O NH2 N N H US 2010/0028444 A1 Feb. 4, 2010 30

-continued 95

N2 N CO OH

96 ()- NV - N )

97 Nin O C Nin O nS N O n1N H

98 NH2 NH2

99 US 2010/0028444 A1 Feb. 4, 2010 31

-continued 100

C C N2 N N N OH VN s

101 S --CCC 102

103

HO O O A.N OH N-( ) N ( ) N ( ) 104

N2 N O S

OH US 2010/0028444 A1 Feb. 4, 2010 32

-continued 105 O ( ) ( ) O

N N ()- 388-KO O Y-K)

106

OH N | | N N O O O O OH N 1N 1N

107 HN NH'

N O C

108

109 US 2010/0028444 A1 Feb. 4, 2010 33

-continued 110

111

112 US 2010/0028444 A1 Feb. 4, 2010 34

0091 Preferably, the azo compound is selected from the group consisting of the azo compounds 1, 3, 5, 6, 30, 78, 59 -continued and 112, and, in particular, 1 (=E123), 3 (=E110), 5 (=E128) E129, Allura Red AC: and 6 (=E129): 6 Na" O

E123, Amaranth: O=SEO

Na O O Na OS/ \-0 /M \,M 1. HO NSN 2 N 2 OH. O

Y\, Nat8. O-1 WO\

OESEO 0092. In this case the combinations hereinafter of two O preferred azo compounds are particularly advantageous: E110/E128, E110/E129, E128/E129, E123/E110, E123/ Na" E128 and E123/E129, in particular E110/E129. (0093 Preferably, these are ACK-Sweetened drinks, pref erably caffeine-comprising drinks, which, in addition to the E110, Orange Yellow S, Sunset Yellow: carotenoid particles, comprise the azo compounds E 110 and 3 E 129. These can comprise further HISs and are particularly O Na" preferably sugar-free and carbohydrate-free. \-0 \ EXAMPLES AND COMPARATIVE \, EXPERIMENTS

HO Examples 1 to 18 The Use of Water-Dispersible Carotenoid Nanopar 22N ticles for Taste Modulation of Sweeteners 0094 For Examples 1 to 17, the substances hereinafter were used.

Sweeteners: (0095 Acesulfame K (ACK) from Fluca Bio Chemika: OFSFO Aspartame (ASP) from Fluca Bio Chemika; O Na" Formulations (A1) to (A3): Formulation (A11): 0096 Components: Water-dispersible nanoparticles of a E128, Red 2G: particle size of 100 to 300 nm determined using electron microscopy images, based on the formulation (A11), 10% by 5 weight of beta-carotene nanoparticles in vegetable oil drop O lets, stabilized by DL-alpha-tocopherol (E307) and embed ded in a matrix of modified food starch (E 1450) and glucose us NH OH h syrup, and also tricalcium phosphate (E 341) as anticaking agent, N Production: For example using the continuous mixing cham O O ber process described by Dieter Horn and Jens Rieger in Na" \ 4. -- “Organische Nanopartikel in wässriger Phase Theorie, Na Experiment und Anwendung Organic nanoparticles in 2 \, / No aqueous phase—theory, experiment and application, in Angewandte Chemie, 2001, Volume 113, pages 4477, right hand column, last paragraph, to 4478, right-hand column, US 2010/0028444 A1 Feb. 4, 2010

first paragraph, and also in the section “4.1.2. Water-insoluble of medium chain length, stabilized by DL-alpha-tocopherol active components, pages 4481 to 4483, and Subsequent (E 307) and ascorbyl palmitate (E304) and emulsified in a spray drying: glycerol/water mixture; Formulation (A12): Formulation (A3): 0097. Components: Water-dispersible nanoparticles of a 0101 Components: Water-dispersible particles having particle size of 100 to 300 nm determined using electron particle sizes between 150 and 850 um; comprising, based on microscopy images, comprising, based on the Formulation the formulation (A3), 10% by weight of beta-carotene nano (A12), 10% by weight of beta-carotene nanoparticles in veg particles, modified Starch, Sucrose, DL-alpha-tocopherol (E etable oil droplets, stabilized by DL-alpha-tocopherol (E 307), ascorbic acid, sodium ascorbate and tricalcium phos 307) and ascorbyl palmitate (E 304) and embedded in a phate (E341); matrix of fish gelatin (protective colloid) and glucose syrup, Production, for example, by grinding in Suspension, and Sub and also tricalcium phosphate (E341) as anticaking agent; sequent spray drying of the resultant particles. Production: For example using the continuous mixing cham ber method described by Dieter Horn and Jens Rieger in AZO Compounds: “Organische Nanopartikel in wassriger Phase Theorie, Experiment und Anwendung Organic nanoparticles in 0102) No. 3: E110, Sunset Yellow from Sigma; aqueous phase—theory, experiment and application, in No. 6: E129, Allura Red from Sigma; Angewandte Chemie, 2001, volume 113, pages 4477, right hand column, last paragraph, to 4478, right-hand column, Cola Drink: first paragraph, and also in the section “4.1.2. Water-insoluble active components, pages 4481 to 4483, and Subsequent (0103 What was termed “Zero cola’ without sweetener spray drying: was produced as follows: 0.104 36 g of cola flavor (cola base from Döhler, Darm Formulation (A13): stadt, article no. 200380), 0098 Components: Water-dispersible nanoparticles of a 0105 7.7 g of orthophosphoric acid 85% ultrapure median particle size of 100 to 300 nm determined using (Karl Roth GmbH+Co. KG, Karlsruhe, article no. 9079. electron microscopy images, based on Formulation (A13), 1), 10% by weight of lycopene nanoparticles in vegetable oil 01.06 3.6 g of citric acid 99.5% p.a. (Karl Roth GmbH+ droplets, stabilized by DL-alpha-tocopherol (E 307) and Co. KG, Karlsruhe, article no. 3958.2), embedded in a matrix of modified food starch (E 1450) and 0.107 2.4 g of sodium benzoate from Fluka, Sigma glucose syrup, and also tricalcium phosphate (E341) as anti Aldrich, Steindrunn, and caking agent; 0.108 1.2 g of caffeine, anhydrous, 99% from Fluka, Production: For example using the continuous mixing cham Sigma-Aldrich, Steindrunn ber method described by Dieter Horn and Jens Rieger in were dissolved in 600 ml of tap water. 50 ml portions of this “Organische Nanopartikel in wassriger Phase Theorie, concentrate were made up in each case to one liter of “Zero Experiment und Anwendung Organic nanoparticles in cola’. aqueous phase—theory, experiment and application, in Angewandte Chemie, 2001, volume 113, pages 4477, right Quantitative Sensory Testing General Protocol: hand column, last paragraph, to 4478, right-hand column, 0109 Consensus profiles of samples 1 to 18 of Examples first paragraph, and also in the section “4.1.2. Water-insoluble 1 to 18 and also of control samples 1 to 6 were prepared in active components, pages 4481 to 4483, and Subsequent agreement with DIN 10967-2/ISO 11035. For this, 8 trained spray drying: testers which had been selected in accordance with the DIN/ ISO provisions were made familiar with the products by Formulation (A14): definition and training of the predetermined feature proper 0099 Components: Water-dispersible nanoparticles of a ties. particle size of 200 to 300 nm determined using electron 0110. Subsequently, the testers tasted the samples 1 to 17 microscopy images; comprising, based on the formulation in order to assess the taste, aftertaste and mouth feel in accor (A14), 10% by weight of beta-carotene nanoparticles in corn dance with the given feature properties. The respective con germ oil droplets, embedded in a matrix of modified food sensus profiles were summarized by the test leader in the form starch; of tables and spider's web diagrams. Hereinafter, for the sake Production, for example using the process described in the of clarity, only the tables are reproduced. textbook by J. C. Bauernfeind, “Carotenoids as Colorants and Vitamin A Precursors. Technological and Nutritional Appli Samples 1 to 18 and Control Samples 1 to 5 Composition of cations”, Chapter 2, J. C. Bauernfeind and H. Klaui, "Caro Matter: tenoids as Food Color, pages 92 to 95, Academic Press, ISBN 0-12-082850-2, 1981, and subsequent spray drying: 0111 Samples 1 to 18 and the control samples 1 to 5 had the compositions of matter described hereinafter. The respec Formulation (A2): tive abbreviations which are used in the tables hereinafter are given in brackets. 0100 O/W microemulsion of a droplet size of 200 nm determined using quasielastic light scattering, comprising, Control Sample 1: based on the formulation (A2), 10% by weight of beta-caro tene dissolved in vegetable oil and triglycerides offatty acids (O112 Water+500 mg/l of ACK (abbreviation: water/ACK) US 2010/0028444 A1 Feb. 4, 2010 36

Control Sample 2: Sample 10 Example 10: 0113 Water+350 mg/l of ASP (abbreviation: water/ASP) (0.126 Zero cola+140 mg/l of ACK+350 mg/l of ASP+ formulation (A12), corresponding to 1 ppm of beta-carotene Control Sample 3: (abbreviation: cola/ACK/ASP/A12) 0114 Water+140 mg/l of ACK+350 mg/l of ASP (abbre viation: water/ACK/ASP) Sample 11—Example 11: I0127. Zero cola--500 mg/l of ACK+formulation (A11), Control Sample 4: corresponding to 1 ppm of beta-carotene, +2.5 mg/l of azo 0115 Zero cola--500 mg/l of ACK (abbreviation: cola? compound E129 ACK) (abbreviation: cola/ACK/A11/E129) Control Sample 5: Sample 12—Example 12: 0116. Zero cola+140 mg/l of ACK+350 mg/l of ASP (ab I0128. Zero cola--500 mg/l of ACK+formulation (A11), breviation: cola/ACK/ASP) corresponding to 1 ppm of beta-carotene, +2.3 mg/l of azo compound E110 Sample 1-Example 1 (abbreviation: cola/ACK/A11/E110) 0117 Water+500 mg/l of ACK+formulation (A11), corre sponding to 1 ppm of beta-carotene (abbreviation: water/ Sample 13—Example 13: ACK/A11) I0129 Zero cola--500 mg/l of ACK+formulation (A11), corresponding to 1 ppm of beta-carotene, +2.3 mg/l of azo Sample 2 Example 2: compound E10+2.5 mg/l of azo compound E129 0118 Water+500 mg/l of ACK--formulation (A13), corre (abbreviation: cola/ACK/A11/E110) sponding to 1 ppm of lycopene (abbreviation: water/ACK/ A13) Sample 14 Example 14: I0130. Zero cola+140 mg/l of ACK+350 mg/l of ASP+ Sample 3—Example 3: formulation (A11), corresponding to 1 ppm of beta-carotene, 0119 Water+500 mg/l of ACK+formulation (A12), corre +2.3 mg/l of azo compound E110 sponding to 1 ppm of beta-carotene (abbreviation: water/ (abbreviation: cola/ACK/ASP/A11/E110) ACK/A12) Sample 15—Example 15: Sample 4 Example 4: I0131 Zero cola+140 mg/l of ACK+350 mg/l of ASP+ 0120 Water+500 mg/l of ACK--formulation (A11), corre formulation (A11), corresponding to 1 ppm of beta-carotene, sponding to 1 ppm of beta-carotene, +2.3 mg/l of azo com +2.3 mg/l of azo compound E110+2.5 mg/l of azo compound pound E10+azo compound 2.5 mg/l of E129 E129 (abbreviation: water/ACK/A11/E110/E129) (abbreviation: cola/ACK/ASP/A11/E110/E129) Sample 5 Example 5: Sample 16—Example 16: 0121 Water+140 mg/l of ACK+350 mg/l of ASP+formu I0132) Water+500 mg/l of ACK--formulation (A14), corre lation (A11), corresponding to 1 ppm of beta-carotene sponding to 1 ppm of beta-carotene (abbreviation: water/ACK/ASP/A11) (abbreviation: water/ACK/A14) Sample 6 Example 6: Sample 17 Example 17: 0122 Water+350 mg/l of ASP+formulation (A11), corre sponding to 1 ppm of beta-carotene 0.133 Water+500 mg/l of ACK--formulation (A2), corre (abbreviation: water/ASP/A11) sponding to 1 ppm of beta-carotene (abbreviation: water/ACK/A2) Sample 7 Example 7: Sample 18 Example 18: (0123 Water+140 mg/l of ACK+350 mg/l of ASP+formu lation (A12), corresponding to 1 ppm of beta-carotene 0.134 Water+500 mg/l of ACK--formulation (A3), corre (abbreviation: water/ACK/ASP/A12) sponding to 1 ppm of beta-carotene (abbreviation: water/ACK/A3) Sample 8 Example 8: 0.124 Zero cola--500 mg/l of ACK+formulation (A11), Samples 1 to 7 and Also 16 to 18 and Control Samples 1 to corresponding to 1 ppm of beta-carotene 3—Experimental Results: (abbreviation: cola/ACK/A11) 0.135 The results of the quantitative sensory testing of samples 1 to 7 and 16 to 18, and also of control samples 1 to Sample 9 Example 9: 3, are summarized in Table 1. The measurement 0 means that 0125 Zero cola+140 mg/l of ACK+350 mg/l of ASP+ the relevant sensory property was not present; the measure formulation (A11), corresponding to 1 ppm of beta-carotene ment 10 means that the relevant sensory property was (abbreviation: cola/ACK/ASP/A11) strongly present. US 2010/0028444 A1 Feb. 4, 2010 37

TABLE 1 Quantitative sensory testing of samples 1 to 7 and 16 to 18, and also control samples 1 to 3 - consensus profile Control sample? Taste Mouth feel Aftertaste sample sa) Bt) Ce) Kd) Bie) A? S(Nyg) Bt(Ny) A(N) C(Ny) Control sample 1 4 O 4 2 3 6 ind O WaterfACK Control sample 2 O O 2 1m) O ic) Water ASP Control sample 3 ic) erfACKASP e 1 ic) KJA11 ic) KA13

KJA12 ic) KA12

ic)

= Sweet: = bitter: = chemical; = prickly; = coating: = drying: 8 S(N) = sweet aftertaste: 'Bt(N) = bitter aftertaste: A(N) = drying out in aftertaste; JCON) = chemical aftertaste; *nd = not determined: first aqueous, then sweet aftertaste; "aftertaste decays rapidly;

0136. From the results of Table 1, the following taste reduced. However, sample 3 was perceived to be somewhat modulating effects were found for samples 1 to 7 in detail: more strongly coating and somewhat less Sweet than sample 1. Sample 1: Sample 4: 0140. The triple combination formulation (A11)/E110/ 0.137 The formulation (A11) reduced the bitter taste and E129 showed synergistic effects in the modulation of the completely reduced the bitter aftertaste of ACK in water. bitter taste and aftertaste. Not only the bitter taste but also the Sample 2: bitter aftertaste were completely reduced. Sample 5: 0.138. The formulation (A13) reduced the bitter aftertaste 0.141. The formulation (A11) only very slightly affected of ACK in water. the taste and aftertaste of ACK/ASP in water. Sample 3: Sample 6: 0142. The formulation (A11) caused scarcely any taste 0.139. The formulation (A12) completely reduced the bit changes of ASP in water. However, the slight bitter taste of ter aftertaste of ACK in water; the bitter taste was slightly ASP in water was no longer perceived. US 2010/0028444 A1 Feb. 4, 2010 38

Sample 7: Sample 18: 0146 The formulation (A3) somewhat reduced the bitter 0143. The formulation (A12) affected only to a very slight aftertaste of ACK in water. In addition, sample 18 tasted extent the taste and aftertaste of ACK/ASP in water. significantly less chemical and was significantly less coating than control sample 1. Sample 16: 0.147. Overall, using the formulations (A11) to (A14) and also (A2) and (A3), in particular in combination with the azo 0144. The formulation (A14) reduced the bitter taste of compounds E 110 and E129, the bitter taste and the bitter ACK in water and completely reduced the bitter aftertaste. In aftertaste of ACK in water were significantly reduced. addition, sample 16 was less coating than control sample 1. Samples 8 to 15 and Control Samples 4 and 5—Experimental Sample 17: Results: 0.148. The results of the quantitative sensory testing of 0145 The formulation (A2) reduced the bitter taste of samples 8 to 15 and control samples 4 and 5 are summarized ACK in water and completely reduced the bitter aftertaste. In in Table 2. The measurement 0 means that the relevant sen addition, Sample 17 was significantly less coating than con sory property was not present; the measurement 10 denotes trol sample 1. that the relevant sensory property was strongly present.

TABLE 2 Quantitative sensory testing of samples 8 to 15 and control samples 4 and 5 - consensus profiles Control probef Taste Mouth feel Aftertaste Probe BSc) SS Bt) KC) Me) Co.) S8) A Bri Au S(N)*) Bt(Ny K(NY) Control sample 4 1 6 4 4 2 4 4 2 4 3 3 1 O cola ACK Control sample 5 4 2 S 6 O 2 6 O 2 cola? ACKASP Samp 4 3 3 3 1 3 3 3 1 2

4 2 4 9 1 3 5 O 2

4 1 4 S O 1 5 O 1

5 4 2 2 O 1 2 O O

4 2 3 4 O 3 3 O O

3 1 5 5 O 2 4 O O

2 O 5 5 O 1 5 O O aACKASP

2 O S 6 O 1 6 O O aACKAS Pf 1.E.129, E1 O BS = beginning of sweetness; S? = acidic; Bt = bitter: KC = artificial/chemical; M = metallic: JCo = cola; 8S = sweet: 'A = astringent; BI = coating: JAu = drying: *S(N) = sweet aftertaste: Bt(N) = bitter aftertaste: "K(N) = prickly aftertaste only on swallowing for about 10 seconds; US 2010/0028444 A1 Feb. 4, 2010 39

0149 From the results of Table 2, in detail, the following tinuous mixing chamber process described by Dieter taste-modulating effects were found for samples 8 to 15. Horn and Jens Rieger in “Organische Nanopartikel in wässriger Phase Theorie, Experiment und Anwend Sample 8: ung Organic nanoparticles in aqueous phase—theory, experiment and application, in Angewandte Chemie, 0150. The formulation (A11) had a beneficial effect on the 2001, volume 113, pages 4477, right-hand column, last modulation of the bitter taste. However, the cola flavor paragraph, to 4478, right-hand column, first paragraph, decreases slightly and the sample has a prickly aftertaste. and also in the section “4.1.2. In Wasser unlösliche Sample 9: Wirkstoffe' Water-insoluble active compounds’. pages 4481 to 4483, and spray drying (abbreviation: 0151. The formulation (A11) only slightly affected the water/ACK/C1), and taste of ACK/ASP in cola. Sample 9 was somewhat less acidic 0.161 in comparative experiment C2, a carotenoid-free and not bitter. It had somewhat less cola flavor but somewhat placebo C2, which had been produced by mixing modi more SWeetness. fied Starch, tocopherol, vegetable oil and glucose and spray drying the resulting mixture (abbreviation: water/ Sample 10: ACK/C2), 0152 The formulation (A12) only slightly affected the were used. taste of ACK/ASP in cola. However, the bitter taste was no 0162 The results of quantitative sensory testing of longer present. samples C1 and C2 of the comparative experiments C1 and C2 are compared in Table 3 with the results obtained with Sample 11: control sample 1. The measurements have the meaning 0153. The formulation (A11) and E129 completely reported above for Tables 1 and 2. reduced the bitter taste and bitter aftertaste of ACK in cola. The Sweet taste and the Sweet aftertaste were somewhat TABLE 3 reduced. Quantitative sensory testing of samples C1 and C2 Sample 12: and control sample 1 - consensus profiles 0154) The formulation (A11) and E110 completely Control sample? Taste Mouth feel Aftertaste reduced the bitter taste and bitter aftertaste of ACK in cola. sample sa) Bt) Ce) Ka Bie) A? S(Ng) Bt(Ny) Sample 12, in addition, was found to be non astringent. The Control sample 1 6 4 4 O 4 2 3 6 cola flavor was only somewhat reduced. water ACK Sample C1 8 6 4 O 2 2 5 2 Sample 13: water ACKC1 Sample C3 7 5 4 O 4 3.5 4 1 (O155 The formulation (A11), E 110 and E129 completely waterfACKC2 reduced the bitter taste and aftertaste of ACK in cola. The S = sweet: other adverse taste attributes (acidic, artificial/chemical, Bt = bitter; metallic, astringent, coating, drying) were reduced, whereas °C = chemical; the favorable taste attributes (sweetness, cola) were K = prickly; improved. BI = coating: /A = drying: 8S(N) = sweet aftertaste: Sample 14: Bt(N) = bitter aftertaste: 0156 The formulation (A11) and E110 somewhat reduced the acidic, bitter, artificial/chemical and metallic taste, and 0163 Comparative experiments C1 and C2 showed that also the prickly aftertaste of ACK/ASP in cola. The Sweetness the beta-carotene-free placebos C1 and C2 somewhat was no longer so intensely pronounced as in control sample 6. increased the bitter taste of ACK in water, whereas they reduced the bitter aftertaste. Sample 15: (O157. The formulation (A11), E110 and E129 somewhat 1-51. (canceled) reduced the acidic, bitter, artificial/chemical and metallic 52. A composition comprising at least one water-dispers taste, and also the prickly aftertaste of ACK/ASP in cola. In ible carotenoid nanoparticle as a taste modulator. addition, sample 15 was less drying than control sample 6. 53. The composition of claim 52, wherein said at least one The bitter aftertaste was not reduced. Otherwise, the positive water-dispersible carotenoid nanoparticle has a particle size taste attributes (sweetness, cola) were not affected. of less than 1 Jum. 54. The composition of claim 52, wherein said at least one Comparative Experiments C1 and C2 water-dispersible carotenoid nanoparticle is liquid or solid. 0158. The use of carotenoid-free placebos C2 and C1 for 55. The composition of claim 54, wherein the carotenoid or taste modulation of Sweeteners carotenoids in said at least one solid water-dispersible caro 0159. Example 1 was repeated, except that, instead of the tenoid nanoparticle are X-ray amorphous. formulation (A11) 56. The composition of claim 54, wherein the carotenoid or 0160 in comparison experiment C1, a carotenoid-free carotenoids in said at least one liquid water-dispersible caro placebo C1, which had been produced from modified tenoid nanoparticle are dissolved in a liquid medium or are starch, tocopherol, vegetable oil and glucose by the con present in the form of a solubilized mixed micelle. US 2010/0028444 A1 Feb. 4, 2010 40

57. The composition of claim 52, wherein said at least one water-dispersible carotenoid nanoparticle is present in a liq uid or solid formulation comprising at least one additive E123: permitted under food law and/or drugs law. 58. The composition of claim 57, wherein said at least one Na" O O Na" additive is selected from the group consisting of protective OS/ \, -O colloids, stabilizers against oxidative breakdown, emulsifi- M V ers, oils, plasticizers, compositions against caking, and poly- O O ols. HO 59. The composition of claim 57, wherein said at least one water-dispersible carotenoid nanoparticle is present in a Solid 2N formulation comprising at least one additive permitted under food law and/or drugs law, wherein said at least one water dispersible carotenoid is embedded in a matrix of at least one additive. 60. The composition of claim 57, wherein said liquid or solid formulation comprises from 0.5 to 30% by weight of OFSFO carotenoid or carotenoids, based on the total weight of said liquid or Solid formulation. 61. The composition of claim 57, wherein said liquid or Na solid formulation comprises from 10 to 80% by weight of a protective colloid, based on the total weight of said liquid or solid formulation. 62. The composition of claim 57, wherein said liquid or E1.10: solid formulation comprises from 20 to 70% by weight of plasticizer, based on on the total weight of said liquid or solid O Nat formulation. \l-O 63. The composition of claim 52, wherein said at least one \ water-dispersible carotenoid nanoparticle reduces the bitter taste and the bitter aftertaste of said composition. HO 64. The composition of claim 52, wherein said composi tion is a food, drink, article consumed for pleasure, Sweeten- 2 N ing agent, animal feed, cosmetic, or pharmaceutical. 65. The composition of claim 52, wherein said composi tion is a low-sugar composition having less than 10g of Sugar per liter or kg of said composition. 66. The composition of claim 52, wherein said composi tion comprises at least one High Intensity Sweetener (HIS) as a Sweetening agent. O 67. The composition of claim 52, wherein said at least one Na" water-dispersible carotenoid nanoparticle is present in an amount Such that a carotenoid concentration in the range of from 0.1 to 100 ppm results. 68. The composition of claim 52, wherein said at least one water-dispersible carotenoid nanoparticle is present in an E128: amount Such that a carotenoid concentration in the range of 5 from 0.1 to 100 mg/l results. 69. The composition of claim 52, wherein said composi- ls tion comprises at least one azo compound comprising at least one azo group, wherein said at least one azo compound NH | reduces the bitter taste and aftertaste of said composition. N 70. The composition of claim 69, wherein said composi tion comprises from 0.1 to 100 ppm of said at least one azo Na' \ M compound based on the total weight of said composition. 71. The composition of claim 69, wherein said at least one O O aZo compound is selected from the group consisting of E 110, E123, E128, and E129: US 2010/0028444 A1 Feb. 4, 2010 41

-continued E129: E123:

Na" -- 1

OH.

Na" 72. The composition of claim 66, wherein said at least one HIS is selected from the group consisting of acesulfame potassium, aspartame, saccharin and salts thereof, cyclamate and salts thereof, aspartame-acesulfame salt, Sucralose, thau E1.10: matin, Stevia, Stevioside, and neohesperidin dihydrochal COC. 3 73. A process for modulating the taste of a composition W-O comprising adding at least one water-dispersible carotenoid S 1. nanoparticle to said composition. O 74. The process of claim 73, wherein said at least one water-dispersible carotenoid nanoparticle is used in an HO amount Such that, when said composition is a solid, a con centration of carotenoid or carotenoids of 0.1 to 100 ppm N results, and when said composition is a liquid, a concentration of carotenoid or carotenoids of 0.1 to 100 mg/l results. 75. The process of claim 73, wherein said composition is a food, drink, article consumed for pleasure, Sweetening agent, animal feed, cosmetic, or pharmaceutical. OFSFO 76. The process of claim 73, wherein said composition is a low-Sugar composition having less than 10g of Sugar per liter O or kg. Na" 77. The process of claim 76, wherein said composition is a Sugar-free composition. 78. The process of claim 73, wherein said compositions comprises at least one High Intensity Sweetener (HIS) as E128: Sweetening agent. 79. The process of claim 73, wherein at least one azo compound comprising at least one azo group and which reduces the bitter taste and aftertaste of said composition is ls further added to said composition. NH OH h 80. The process of claim 79, wherein from 0.1 to 100 ppm N of said at least one azo compound is added to said composi tion, based on the total amount of said at least one azo com- Na" R / pound and said composition. 21 V 7 No Na 81. The process of claim 79, wherein said at least one azo O O compound is selected from the group consisting of E 110, E123, E128, and E129: US 2010/0028444 A1 Feb. 4, 2010 42

91. The taste modulator of claim 90, wherein said at least -continued one additive is selected from the group consisting of protec E129: tive colloids, stabilizers against oxidative breakdown, emul 6 sifiers, oils, plasticizers, compositions against caking, and O Na" polyols.

O=SEO 92. The taste modulator of claim 90, said at least one water-dispersible carotenoid nanoparticle is present in a solid formulation which comprises at least one additive permitted under food law and/or drugs law, wherein said at least one 1 water-dispersible carotenoid nanoparticle is embedded in a matrix of said at least one additive. s 93. The taste modulator of claim 90, wherein said liquid or solid formulation comprises from 0.5 to 30% by weight of OH. carotenoid or carotenoids, based on the total weight of said liquid or Solid formulation. \ 94. The taste modulator of claim 90, wherein said liquid or Na O 1 \, solid formulation comprises from 10 to 80% by weight of a protective colloid, based on the total weight of said liquid or solid formulation. 95. The taste modulator of claim 90, wherein said liquid or solid formulation comprises from 20 to 70% by weight of a 82. The process of claim 78, wherein said at least one HIS plasticizer, based on the total weight of said liquid or Solid is selected from the group consisting of acesulfame-potas formulation. sium, aspartame, saccharin and salts thereof, cyclamate and 96. The taste modulator of claim 84, wherein said at least salts thereof, aspartame-acesulfame salt, sucralose, thauma one azo group is linked to an aryl group. tin, and neohesperidin dihydrochalcone. 97. The taste modulator of claim 96, wherein said aryl 83. The process of claim 73, wherein the bitter taste and the group is a phenyl group and/or a naphthyl group. bitter aftertaste of said composition is reduced as a result of 98. The taste modulator of claim 96, wherein said aryl the taste modulation. group is Substituted by at least one Sulfonic acid group and/or 84. A taste modulator for a composition which comprises at least one hydroxyl group. (A) at least one water-dispersible carotenoid nanoparticle: 99. The taste modulator of claim 96, wherein said at least and one azo compound is selected from the group consisting of (B) at least one azo compound comprising at least one azo E110, E123, E128, and E129: group. 85. The taste modulator of claim 84, wherein the weight ratio of (A) to (B) is in the range of from 10:1 to 1:20. 86. The taste modulator of claim 84, wherein said at least E123: one water-dispersible carotenoid nanoparticle has a particle 1 size of less than 1 Jum. Na" O O Na" 87. The taste modulator of claim 84, wherein said at least OS/ \-0 one water-dispersible carotenoid nanoparticle is liquid or M V solid. / \, 88. The taste modulator of claim 87, wherein said at least HO one water-dispersible carotenoid nanoparticle is solid and the carotenoid or carotenoids in said solid nanoparticle are X-ray 2a N amorphous. 89. The taste modulator of claim 87, wherein said at least one water-dispersible carotenoid nanoparticle is liquid and the carotenoid or carotenoids in said liquid nanoparticle are dissolved in a liquid medium or are present in the form of a solubilized mixed micelle. OFSFO 90. The taste modulator of claim 84, wherein said at least O one water-dispersible carotenoid nanoparticle is present in a Na" liquid or Solid formulation which comprises at least one addi tive permitted under food law and/or drugs law. US 2010/0028444 A1 Feb. 4, 2010 43

-continued -continued E1.10: E129: 6 Na" O Na" O \-0 O=SEO \,M

HO 1. 2N2 NS. N

OH. O\, OFSFO Nat O1 \, O 100. The composition of claim 52, wherein said composi Na" tion is a low-carbohydrate composition. E128: 101. The composition of claim 52, wherein said composi tion is a carbohydrate-free composition. 102. The composition of claim 52, wherein said composi O tion is an ACK-Sweetened drink. 103. The composition of claim 102, wherein said ACK Sweetened drink comprises caffeine. -- OH h 104. The process of claim 73, wherein said composition is a low-carbohydrate composition. N 105. The process of claim 73, wherein said composition is a carbohydrate-free composition. O O 106. The process of claim 73, wherein said composition is Na" Y. 4. an ACK-Sweetened drink. Na 107. The process of claim 106, wherein said ACK-Sweet 21 \, / No ened drink comprises caffeine.

c c c c c