Classifications

• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
  • C12C5/00—Other raw materials for the preparation of beer
  • C12C5/02—Additives for beer
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
  • A23L2/52—Adding ingredients
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
  • A23B2/729—Organic compounds; Microorganisms; Enzymes
  • A23B2/771—Organic compounds containing hetero rings
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; PREPARATION THEREOF
  • A23C9/00—Milk preparations; Milk powder or milk powder preparations
  • A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
  • A23G3/32—Processes for preparing caramel or sugar colours
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
  • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
  • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
  • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
  • A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
  • A23L2/52—Adding ingredients
  • A23L2/58—Colouring agents
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
  • A23L2/52—Adding ingredients
  • A23L2/60—Sweeteners
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/21—Synthetic spices, flavouring agents or condiments containing amino acids
  • A23L27/215—Synthetic spices, flavouring agents or condiments containing amino acids heated in the presence of reducing sugars, e.g. Maillard's non-enzymatic browning
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
  • A23L5/40—Colouring or decolouring of foods
  • A23L5/41—Retaining or modifying natural colour by use of additives, e.g. optical brighteners
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
  • A23L5/40—Colouring or decolouring of foods
  • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
  • A23L5/40—Colouring or decolouring of foods
  • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
  • A23L5/47—Addition of dyes or pigments, e.g. in combination with optical brighteners using synthetic organic dyes or pigments not covered by groups A23L5/43 - A23L5/46
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents

Definitions

• the present invention relates to a beverages and foodstuffs having heightened resistance to light induced flavour changes, and compositions that can be used advantageously as additives in beverages or foodstuffs to prevent or reduce light induced flavour changes.
• the products and compositions according to the invention contain caramelised carbohydrate of low colour intensity.
• the present invention is particularly suitable for use in beverages or foodstuffs that are prone to developing an off-flavour as a result of exposure to light, and especially in such beverages or foodstuffs that are not adequately protected from the detrimental impact of light by their packaging.
• the present invention also includes a process for the manufacture of such beverages and foodstuffs, using such compositions.
• Light induced off-flavour formation is a well known problem in the beverage and food industry.
• a variety of off-flavour generating reactions that are initiated or accelerated by exposure to light have been described in the scientific literature.
• the rate at which these off-flavour generating reactions progress is usually increased dramatically by exposure to light with a wavelength below 500 nm, particularly UV- light.
• Light sensitive flavour changes in beverages and foodstuffs may be inhibited effectively by packaging these beverages or foodstuffs in a material that will not transmit light frequencies that promote off-flavour generating reactions.
• the composition of the beverage or foodstuff will need to be optimised to achieve sufficient stability against light induced flavour changes.
• special light stabilising additives may be used. It is known in the art to employ a large variety of additives for the stabilisation of beverages and food products against light induced off-flavour formation. Many of these additives derive their effectiveness from their capability to inhibit off-flavour generating reactions, e.g. by scavenging of one or more of the reactants and/or key intermediates. In addition, additives have been proposed that scavenge the off-flavour causing reaction products (e.g.
• US 5,948,458 describes a method for the prevention of spoilage, rancidity or off-color in a liquid food product containing unsaturated lipids and fats caused by exposure of the liquid food product to ultraviolet light comprising the step of adding to said food product an ultraviolet absorbing effective amount of tricalcium phosphate.
• US 4,389,421 teaches the addition of organic compounds containing 1,8-epoxy groups, such as 1,8-cineole, to prevent or significantly reduce light struck flavour in malt beverages. It is hypothesised therein that the addition of 1,8-epoxy compounds to malt beverages prevents the formation of methyl butenyl mercaptan by preventing cleavage of a five carbon fragment (iso-pentenyl chain) from the iso-hexenoyl side chain of iso- ⁇ -acids, which fragments would otherwise react with the sulfhydryl group forming the iso-pentenyl mercaptan (methyl butenyl mercaptan).
• 1,8-epoxy compounds to malt beverages prevents the formation of methyl butenyl mercaptan by preventing cleavage of a five carbon fragment (iso-pentenyl chain) from the iso-hexenoyl side chain of iso- ⁇ -acids, which fragments would otherwise react
• the 1,8-epoxy compounds may prevent formation of methyl butenyl mercaptan by reacting with the iso-pentenyl fragment or by protecting the iso-hexenoyl side chain from fragmenting or by blocking the sulfhydryl group from reacting with the iso-pentenyl fragment.
• Many food additives that have been proposed for stabilising beverages or foodstuffs against light induced off-flavour formation have to be labelled as chemical or artificial entities on the product package. With a view to consumer acceptance manufacturers of beverages and foodstuffs generally do not like to use such chemical additives but, instead, prefer to employ additives that make more appealing ingredient labels (consumer-friendly labels) possible and that deliver similar functionality.
• caramelised carbohydrate such as caramel
• the inventors have discovered that improved resistance to light induced flavour changes may be imparted to beverages and foodstuffs by compositions that comprise caramelised carbohydrate of low colour intensity.
• caramelised carbohydrate such as caramel
• caramelisation i.e. the reaction occurring when carbohydrates are heated, yields reaction products exhibiting the capability to absorb ultraviolet light without being decomposed into undesirable off- flavour generating substances, especially if the carbohydrates are caramelised in the presence of a nitrogen source.
• the inventors have found that these UV-absorbing substances, unlike other intrinsic constituents of caramelised materials, are essentially colourless. Thus, based on this knowledge, the inventors have developed a composition that can be used to stabilise beverages or foodstuffs against light induced flavour changes without introducing a substantial colour change. Although the inventors believe that the advantageous properties of the present composition are mainly associated with its UV-absorbing properties, it is possible that the protective properties of the present composition are partially derived from other qualities.
• the present products and light stabilising compositions contain caramelised carbohydrate of low colour intensity and combines a relatively high absorption of UV light, particularly at wavelengths in the range of 250 to 400 nm, with a relatively low absorption of visible light, as demonstrated by a ratio of the light absorption at wavelengths 280 nm and 560 nm (A 28 o/ 560 ) of at least 200.
• the caramelised carbohydrate of low colour intensity is suitably prepared by decolourising caramel to remove the components responsible for the brown colour whilst retaining the UV absorbing components, as demonstrated by an increase of A 8 o /56 o by at least 100%.
• the caramelised carbohydrate may be prepared by selecting reaction conditions that favour formation of the UV absorbing components (e.g.
• caramels that have been produced by caramelisation in the presence of a nitrogen source are commonly characterised on the basis of the so called extinction ratio (the abso ⁇ tion ratio A 280/ 5 60 ) which is determined by the method described below under "Classification/ Absorbance ratio". Typically, these caramels exhibit an absorption ratio A 28 o /56 o of less than 120. Decolourisation of caramels in accordance with the present invention removes coloured components that absorb at around 560 nm whilst at the same time retaining its UV-absorption characteristics.
• decolourisation of caramels in accordance with the invention produces a material with a significantly higher absorption ratio A 280/560 than ordinary caramels that have been produced by caramelisation in the presence of a nitrogen source (notably ammonia caramel and sulphite ammonia caramel).
• a nitrogen source notably ammonia caramel and sulphite ammonia caramel.
• one aspect of the present invention is concerned with a composition
• a composition comprising caramelised carbohydrate, which composition, when dissolved in water at a dry solids content of 0.1 wt.%, exhibits: i. an absorption at 280 nm (A 280 ) that exceeds 0.01, preferably exceeds 0.05, more preferably exceeds 0.1 and most preferably exceeds 0.3; and ii. an absorption ratio A 28 o/5 6 0 of at least 200, preferably of at least 250.
• the caramelised carbohydrate of the invention differs from ordinary caramels by its relatively low content of colour components, notably brown colour components. The low content of colour components is evident from the relatively low absorption at 560 nm (A 56 o).
• the caramelised carbohydrate exhibits strong UV abso ⁇ tion capacity as evidenced by the present composition's A 280 .
• the present caramelised carbohydrate as well as the present composition are characterised by a relatively high abso ⁇ tion ratio A 80 / 56 o-
• the present composition typically contains at least 10%, preferably at least 20%, more preferably at least 30%, even more preferably at least 40% and most preferably at least 50% of the caramelised carbohydrate by weight of dry solids.
• the A 280 is determined relative to %solids as described herein below under “Colour intensity", except that the absorbance is measured at 280 nm instead of 610 nm.
• the term "wavelength” as used in here, refers to a wavelength of light, unless indicated otherwise.
• Caramelisation is commonly defined as the thermal degradation of sugars leading to the formation of volatiles (caramel aroma) and brown-coloured products (caramel colours).
• the process is acid or base catalysed and generally requires temperature in excess of 120°C at a pH within the range of 3 and 9.
• the generation of flavours and colours in thermally induced caramelisation requires that sugars, normally monosaccharides, first undergo intramolecular rearrangements. Usually, the reaction causes the release of H + . Thus, the pH of a solution undergoing caramelisation falls with time. Caramelisation occurs in a complex sequence of reactions.
• the initial enolisation reaction is of particular importance because it initiates the subsequent chain of events. These reactions give rise to sugar degradation products which can react further to produce oxygen heterocyclic and carbocyclic compounds via aldol condensation.
• the key intermediates of the themal caramelisation are the osuloses. These are ⁇ -dicarbonyl compounds such as 3-deoxyhexosulose. These substances not only lead to the formation of caramel colour but also give rise to the important volatile products which are typical of caramel flavour.
• caramelised carbohydrates, and especially caramels obtained by caramelisation in the presence of a nitrogen source are particularly suitable for use in accordance with the present invention.
• Caramels so obtained are characterised by the presence of significant quantities of cyclic nitrogen containing components, such as pyrazine derivatives.
• the inventors have observed a strong positive correlation between the effectiveness of the present composition in stabilising beverages and foodstuffs against light induced flavour changes and its content of N-heterocyclic substances.
• the present composition contains at least 0.5%, preferably at least 1.0%, more preferably at least 3.0% by weight of dry matter, of N-heterocyclic substances. It was found that N- heterocyclic substances of which the ring(s) contains at least two nitrogen atoms exhibit particularly good light stabilising properties. Aromatic N-heterocyclic substances, particularly those containing two nitrogen atoms, are particularly preferred.
• the N-heterocyclic substances are selected from the group consisting of pyrazines, pyrimidines, pyridazines, and combinations thereof.
• the N-heterocyclic substances according to the present invention preferably exhibit a water solubility of at least 10 mg/kg, more preferably of at least 100 mg/kg.
• the molecular weight of said substances typically does not exceed 500, preferably it does not exceed 400, more preferably it does not exceed 350.
• the inventors have observed that the present composition produces particularly good results if the caramelised carbohydrate contains a significant amount of pyrazine derivatives, particularly pyrazine derivatives that comprise carbohydrate derived substituents.
• the present composition contains at least 0.5%, preferably at least 1.0%, more preferably at least 3.0% by weight of dry matter, of pyrazine derivatives according to formula (I):
• R1-R 4 independently represent hydrogen; a hydroxyhydrocarbyl residue; an ester of a hydroxyhydrocarbyl residue; or an ether of a hydroxyhydrocarbyl residue; and at least one of Rn - R 4 is a hydroxyhydrocarbyl residue or an ester or an ether thereof.
• at least one of Rr-R4 represents a hydroxyhydrocarbyl residue or an ester thereof, more preferably it represents a hydroxyhydrocarbyl residue.
• the present invention encompasses all stereoisomers that can be represented by the formulas presented herein. Thus, the present invention may employ racemic mixtures of the present N-heterocyclic substances as well as essentially pure enantiomers of said substances.
• R ⁇ - R 4 is a hydroxyhydrocarbyl residue or an ester or an ether thereof.
• the pyrazine derivative contains two hydroxyhydrocarbyl residues, it is preferred that these residues are in the para or meta positions.
• two of Ri - R 4 are a hydroxyhydrocarbyl residue or an ester or an ether thereof.
• hydroxyhydrocarbyl refers to hydroxyl substituted hydrocarbyls.
• hydrocarbyl refers to branched and linear hydrocarbon chains, optionally containing one or more unsaturated carbon-carbon bonds, i.e.
• hydroxyhydrocarbyls include branched as well as unbranched hydroxyalkyls and hydroxyalkenyls.
• the hydroxycarbyl residue may also comprise other substituents such as carbonyl, carboxyl, acyl, amino, acylamino, alkoxy, hydroxyamino, alkoxyamino, thiol, disulfide, ether, ester, alkylthio and amide groups.
• the latter substituents contain not more than 10, more preferably not more than 5 carbon atoms.
• the hydrocarbyl residue does not contain substituents other than one or more hydroxyl groups.
• the hydroxyhydrocarbyl residue comprises 1-10, preferably 2-4 carbon atoms, and more preferably 3 or 4 carbon atoms.
• the total number of carbon atoms present in the pyrazine derivatives is within the range of 5-12, more preferably within the range of 9-12.
• the at least one hydroxyhydrocarbyl residue preferably comprises at least two hydroxyl groups. More preferably, said residue comprises three or four hydroxyl groups.
• the pyrazine derivatives in the light stabilising composition of the present invention typically contain a high fraction of di-substituted pyrazines.
• the present composition contains at least 0.5% by weight of dry matter of pyrazine derivatives according to formula (I), wherein at least two of R ⁇ -R t independently represent a hydroxyhydrocarbyl residue or an ester or an ether thereof.
• di-substituted pyrazine derivatives that are particularly abundant in the present composition include fructosazines, particularly 2,5- and 2,6-substituted fructosazines.
• the present composition contains at least 0.1%, more preferably at least 0.3%, even more preferably at least 0.5%) and most preferably at least 1.0% of a fructosazine selected from the group consisting of 2,5-deoxyfructosazine (l-[5-(2,3,4-trihydroxybutyl)-pyrazin-2-yl]-butane- 1,2,3,4-tetraol), 2,6-deoxyfructosazine (l-[6-(2,3,4-trihydroxybutyl)-pyrazin-2-yl]- butane-1 ,2,3,4-tetraol), 2,5-fructosazine (1 -[5-(l ,2,3,4-tetrahydroxybutyl)-pyrazin-2- yl]-butane-l,2,3,4-tetraol), 2,6-fructosazine (l-[6-(l,2,3,4-tetrahydroxybutyl)-pyrazin-2
• the fructosazine is selected from the group consisting of 2,5-deoxyfructosazine, 2,6-deoxyfructosazine and combinations thereof.
• the fructosazine is selected from the group consisting of l-[6-(2,3,4- trihydroxybutyl)-pyrazin-2-yl]-butane-l,2,3,4-tetraol, l-[5-(2,3,4-trihydroxybutyl)- pyrazin-2-yl] -butane- 1,2,3,4-tetraol and combinations thereof.
• the latter deoxyfructosazines are represented by the following formulae:
• the present invention encompasses the use in beverages or foodstuffs of both synthetic (artificial) and natural pyrazine derivatives, the latter being most preferred.
• synthetic artificial
• natural is used to indicate that such a pyrazine derivative is obtained from a natural source, i.e. it is not obtained by reaction of (petro)chemicals.
• the present composition when obtained by caramelising sugars in the presence of a nitrogen source, will usually contain a significant amount of aminosugars such as glucosamine and fructosamine.
• the composition will typically contain at least 0.001%, preferably at least 0.01%, more preferably at least 0.03%, most preferably at least 0.05% aminosugars, particularly aminosugars comprising mono- or disaccharide residues, more particularly aminosugars comprising a monosaccharide residue.
• the latter percentages being calculated as % by weight on dry matter of the composition.
• the present composition is suitable for stabilising a wide variety of beverages and food products against light induced flavour changes. Best results, however, are obtained in water containing food products, particularly water-continuous food products. In order to avoid that the use of the present composition in these products will cause precipitation, it is preferred that the present stablising composition is essentially completely water soluble.
• the present composition is essentially completely water soluble up to a dry solids content of at least 0.01 wt.%, more preferably up to a dry solids content of at least 0.05 wt.%, most preferably of at least 0.1 wt.%.
• the present light stabilising composition contains not more than minor amounts of the melanoidins that are largely responsible for the brown colour of caramelised materials. Melanoidins are relatively large molecules that can suitably be removed after completion of the caramelisation reaction by means of filtration or another separation technique that enables separation on the basis of molecular weight, size, hydrophobicity or charge.
• the resulting composition typically contains less than 30%, preferably less than 20%, more preferably less than 15%, even more preferably less than 10% and most preferably less than 5%, by weight of dry matter, of components having a molecular weight in excess of 30 kDa. More particularly, the aforementioned amounts relate to the components having a molecular weight in excess of 10 kDa, even more particularly in excess of 5 kDa and most particularly in excess of 1 kDa. The amount of components with a molecular weight in excess of 30 kDa contained in the present composition is determined by passing an aqueous solution of said composition over a Millipore® YM30 filter.
• Millipore® YM10 arid YM1 filters may be used to determine contents of components with a molecular weight in excess of 10 kDa and 1 kDa respectively. It is noted that different techniques for determining the content of high molecular components may yield different results. Therefore, it should be understood that the kDa numbers recited within this application are defined in relation to the methodology described above.
• the reduced level of melanoidins and other colour contributing substances is also evident by a low colour intensity, particularly at wavelengths around 600 nm.
• the present light stabilising composition has a colour intensity at 610 nm that does not exceed 0.024, preferably does not exceed 0.01 as calculated herein.
• the present composition is advantageously provided in a relatively concentrated form, e.g. with a solids content of at least 10 wt.%. More preferably, the solids content is at least 20 wt.%, most preferably at least 30 wt.%.
• the present composition may take the form of a liquid, a syrup, a paste, a powder, granules or tablets.
• the present composition contains less than 80 wt.%, more preferably less than 70 wt.% water.
• the present composition suitably contains nitrogen substances.
• the amount of nitrogen substances in the present composition is limited. Consequently, in a preferred embodiment, the total nitrogen content of the present composition, as determined by Nitrogen Determination (Kjeldahl Method), Method II (FNP 5), is less than 20%, more preferably less than 15%, most preferably less than 10%) by weight of dry matter. In another preferred embodiment, said nitrogen content is at least 0.1%, more preferably at least 0.2% by weight of dry matter.
• the light stabilising composition according to the invention may suitably include additives such as anti-oxidants, emulsifiers and carrier materials.
• the present composition does not contain any ingredients that are not considered “natural", i.e. that need to be labelled as “artificial", “synthetic” or "chemical".
• the entire present composition can be labelled as "caramel”, “caramel colour”, “caramel isolate”, “caramel extract” or the like.
• Another aspect of the present invention is concerned with the use of the present light stabilising composition as an additive to prevent or reduce light induced flavour changes in beverages or foodstuffs.
• the present composition is introduced into the beverage or foodstuff in an amount of at least 0.01 wt.%, preferably of at least 0.02 wt.% and more preferably of at least 0.03 wt.%, calculated on the basis of the amount of dry matter introduced.
• the amount introduced will not exceed 1 wt.%), preferably it will not exceed 0.5 wt.%, more preferably it will not exceed 0.3 wt.%), again calculated on the basis of the amount of dry matter introduced.
• the present composition is particularly suitable for preventing light induced flavour changes in beverages and foodstuffs that contain significant quantities of riboflavin, which substance can act as a photo-initiator.
• the composition is particularly advantageously used in beverages and foodstuffs that contain at least 10 ⁇ g/kg (ppb) riboflavin, more preferably at least 50 ⁇ g/kg riboflavin and most preferably at least 100 ⁇ ,g/kg riboflavin.
• the light stabilising composition according to the invention advantageously contains substantial amounts of pyrazine derivatives.
• the present composition is introduced into beverages or foodstuffs in such an amount that the resulting product contains at least 0.5 mg/kg preferably at least 1 mg/kg, more preferably at least 3 mg/kg and most preferably at least 10 mg/kg of the pyrazine derivatives as defined herein before.
• the malt beverage contains at least 0.5 mg/kg, preferably at least 1 mg/kg of a fructosazine selected from the group consisting of 2,5-deoxyfructosazine, 2,6- deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• a fructosazine selected from the group consisting of 2,5-deoxyfructosazine, 2,6- deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• the benefits of the present light stabilising composition are particularly pronounced if said composition is used to stabilise bottled beverages.
• the term "bottled beverage” encompasses beverages in glass containers (e.g. bottles, jars etc.) as well as beverages in light-transparent plastics, such as plastics based on polyethylene (e.g.
• the present light stabilising composition is used as an additive, particularly a light stabilising additive, in beverages bottled in green, clear (e.g. flint) or blue glass. Most preferably, it is used as an additive in beverages bottled in green or clear glass.
• the present invention encompasses the use of the light stabilising composition in a wide variety of beverages, including beer, soft drinks, liquor, juices, dairy drinks etc.
• the composition is used to prevent or reduce light induced flavour changes in malt beverages, such as beer, ale, malt liquor, porter, shandy, and others which are made from or contain fermented extracts of malt.
• the present light stabilising composition is particularly advantageously employed to improve light stability of beer, more preferably of relatively pale beer, e.g. beer with an EBC colour value of less than 25, more preferably of less than 15, most preferably of less than 12.
• EBC colour value is described below.
• sunstruck formation in beer is promoted particularly strongly by light with a wavelength of 250-550 nm. In general it can be said, the shorter the wavelength the higher the rate at which sunstruck flavour is formed. It is believed that volatile sulphur-containing compounds are responsible for the sunstruck flavour.
• sulphur-containing compounds are thought to be formed at least in part by reaction of other sulphur-containing compounds with photochemically degraded hop components in the beverage. Extremely small quantities of these sulphur compounds are sufficient to impart a sunstruck flavour to a beverage and to render it less acceptable for the consumer (cf. for example Kirk-Othmer, Encyclopedia of Chemical Technology, 4 th Ed., Vol. 4, pages 22 - 63, 1992 and US Patent Application No. 2002/0106422).
• the photochemical reaction leading to the sulphur-containing substances that cause sunstruck flavour is believed to be assisted by the presence of riboflavin. Riboflavin can act as a photo initiator in a beverage and is present in beer in significant quantities.
• Riboflavin in beer emanates mainly from the malt used therein. To a lesser extent also hops and the action of yeast during the fermentation can contribute to the riboflavin content of beer (cf. for example "Kinetics of Riboflavin Production by Brewers Yeast" by Tamer et al., pages 754-756 Enzyme Microb. Technology, 1988, . Vol. 10, December).
• riboflavin in beer
• Recomposition e.g.
• riboflavin present in the beer may also be reduced by treating the beer with absorbent clay (US 6,207,208) or by co-fermenting with a combination of yeast and Leuconostoc mesenteroides (US 6,514,542). It has also been suggested to use immobilised riboflavin-binding protein to remove riboflavin or to add said protein to a beverage to inactivate riboflavin (EP-A 0 879 878).
• the present light stabilising composition is particularly effective in preventing the development of sunstruck flavour in beer, especially in beer that is stored in a container that is transparent to light, particularly a container that is transparent to light with a wavelength in the range of 330-360 nm, more particularly a container that is transparent to a wider spectrum of light within the range of 320-400 nm.
• a principal source of the sunstruck flavour in beer is 3-methyl-2-butene-l-thiol (3-MBT).
• the sensory threshold value for this substance in water is only a few ng/kg (ppt).
• 3-MBT is believed to be formed by the reaction between light excited riboflavin (largely originating from the malt component) and the bittering principles in beer, the iso- ⁇ -acids, which originate mainly from hop.
• the use of the present light stabilising composition in an effective amount to inhibit light induced flavour changes is evident by a reduction in the rate of 3-MBT formation by at least 30%, preferably by at least 50%), more preferably at least 60%, even more preferably at least 70% and most preferably by at least 80%.
• a suitable method for determining the reduction in MBT formation is described in the Examples.
• Yet another aspect of the present invention relates to a process for the manufacture of a composition that may suitably be used as an additive to improve the stability of beverages or foodstuffs against light induced flavour changes, said process comprising the steps of:
• Decolourising said feedstock so as to increase its A 280/560 by at least 100%.
• Decolourisation of the caramelised feedstock may be achieved by any technique known in the art that enables the selective isolation from said feedstock of a light stabilising composition as defined herein before, or that enables selective elimination of the colouring substances present in the caramelised feedstock, e.g. by bleaching. Examples of suitable isolation techniques include: treatment with an adsorbent material (e.g. reversed phase sorbents), filtration and chromatography.
• an adsorbent material e.g. reversed phase sorbents
• the decolourising is achieved by filtration over one or more filters with a cut-off of not more than 30 kDa, preferably of not more than 10 kDa, more preferably of not more than 5 kDa and most preferably of not more than 1 kDa.
• decolourisation is achieved by adso ⁇ tion of the colouring substances onto a reversed phase sorbent, particularly an alkyl-bonded silica or onto cation exchange resin.
• decolourising is achieved by means of liquid chromatography, preferably by means of reversed phase or cation exchange chromatography.
• the caramelised feedstock may comprise high molecular products that are hardly soluble in aqueous systems.
• the present process yields a composition that is essentially completely water soluble, meaning that said process comprises an additional step of removing and/or solubilising insoluble matter if this is required to achieve said water solubility.
• the insoluble matter may suitably be solubilised by e.g. sonication or by adding solvent.
• the optional removal or solubilisation of insoluble matter is preferably carried out prior to decolourisation. It is noted that the present invention also encompasses a process wherein decolourisation and removal of insolubles are achieved in a single step, e.g. by filtration.
• the present invention also encompasses a process wherein the feedstock contains caramel in combination with one or more other brewing adjuncts, e.g. malt, malted barley, syrup.
• Particularly suitable caramels for the present process are caramels as defined in the European Union Directive 95/45; Purity Criteria concerning Colours for use in Foodstuffs and as defined in US Food Chemical Codex IV.
• the caramelised feedstock contains at least 50% by weight of dry matter of brewing adjuncts, including at least 5% caramel by weight of dry matter. More preferably, the feedstock contains at least 10%, even more preferably at least 30% and most preferably at least 50% caramel by weight of dry matter.
• Caramel is a complex mixture of compounds, some of which are in the form of colloidal aggregates.
• Caramel is manufactured by heating carbohydrates either alone or in the presence of food-grade acids, bases, and/or salts.
• Caramel is usually a dark brown to black liquid or solid having an odour of burnt sugar and a somewhat bitter taste.
• Caramel is produced from commercially available food-grade nutritive sweeteners including fructose, dextrose (glucose), invert sugar, sucrose, lactose, molasses and/or starch hydrolysates and fractions thereof.
• the acids that may be used are food-grade sulphuric, sulphurous, phosphoric, acetic and citric acids, and suitable bases are ammonium, sodium, potassium and calcium hydroxides.
• Salts that may be used include ammomum, sodium and potassium carbonate, bicarbonate, phosphate (including mono- and dibasic), sulphate, and sulphite.
• Caramel is soluble in water.
• Four distinct classes of caramel can be distinguished by the reactants used in their manufacture and by specific identification tests (see European Union Directive 95/45 Purity Criteria concerning Colours for use in Foodstuffs and the US Food Chemical Codex TV):
• Class I plain caramel, caustic caramel; E 150a. Class I caramels are prepared by heating carbohydrates with or without acids, bases or salts, but in the absence of ammonium or sulphite compounds. • Class LI: caustic sulphite caramel; E 150b. Class II caramels are prepared by heating carbohydrates with or without acids or bases in the presence of sulphite compounds, but in the absence of ammonium compounds.
• Class LU ammonia caramel
• E 150c Class ffi caramels are prepared by heating carbohydrates with or without acids or bases in the presence of ammonium compounds, but in the absence of sulphite compounds.
• Class IV caramels are prepared by heating carbohydrates with or without acids or bases in the presence of both sulphite as well as ammonia compounds.
• Ammonium compounds that are used in class III and TV caramels include ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium sulphate, ammonium sulphite and ammonium hydrogen sulphite.
• the sulphite compounds are for example sulphurous acid, potassium, sodium and ammonium sulphites and potassium, sodium, ammonium hydrogen sulphites.
• food-grade anti-foaming agents may be used as processing aids.
• ammonia caramel (class IH) constitutes an excellent starting material for the production of a light stabilising composition according to the invention.
• the decolourisation step employed in accordance with this invention does not result in a significant removal or elimination of substances that inhibit sunstruck formation, but merely removes or eliminates substances that absorb in the visible area.
• the decolourisation largely preserves the abso ⁇ tion characteristics of the decolourised material at those wavelengths associated with light induced off-flavour formation. This preservation of, mostly UV-light blocking compounds is best expressed by the 280/560 ratio (A 80/560 ).
• the decolourised caramelised carbohydrate containing composition obtained from the present process typically has an A 280 /5 6 o of more than 200, preferably of more than 250, more preferably of more than 350, more preferably of more than 400, even more preferably of more than 500 and most preferably of more than 1000.
• caramel must have a colour intensity at 610 nm of 0.01-0.6.
• the colour intensity of the caramel containing feedstock used in the present process preferably exceeds 0.01, more preferably exceeds 0.024 on a dry weight basis.
• the colour intensity of the feedstock is preferably reduced by at least a factor 5, more preferably by at least a factor 10 and most preferably by at least a factor 20 as a result of the decolourisation.
• the present process will usually produce a considerable yield in the form of the present light stabilising composition. Typically, the yield of the present process is in the range of 5-90%, especially in the range of 10-80%.
• the present process yields a light stabilising composition in accordance with the present invention in a yield of at least 20%.
• Another aspect of the invention is concerned with a beverage or foodstuff that exhibits improved stability towards light induced flavour changes, wherein the beverage or foodstuff is obtained or obtainable by a method of manufacture that comprises introducing the present light stabilising composition into said beverage or foodstuff.
• the invention relates to such a beverage or foodstuff that contains at least 0.5 mg/kg preferably at least 1 mg/kg, more preferably at least 3 mg/kg and most preferably at least 10 mg/kg of pyrazine derivatives as defined herein before.
• the beverage or foodstuff obtainable by the present method contains at least 0.5 mg/kg, preferably at least 1 mg/kg of a fructosazine selected from the group consisting of 2,5-deoxyfructosazine, 2,6- deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• a fructosazine selected from the group consisting of 2,5-deoxyfructosazine, 2,6- deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• Yet another aspect of the invention relates to a hop containing beverage that is resistant towards light induced flavour changes, said hop containing beverage being characterised by an EBC colour value of less than 25, preferably of less than 15, more preferably of less than 12, and a content of the pyrazine derivatives as defined herein before, expressed in mg/kg, that exceeds 0.1 x EBC colour value, more preferably exceeds 1 x EBC colour value. Even more preferably, said content exceeds 5 x EBC colour value, most preferably 10 x EBC colour value.
• the hop containing beverage is a fermented cereal based beverage.
• the hop containing beverage is beer, malt liquor, porter, shandy, or another beverage made from or containing extracts of hop. Even more preferably, the beverage is beer, most preferably lager beer.
• the hop containing beverage has a yellow or yellowish colour, i.e. it does not have a brownish colour associated with the use of significant amounts of colouring caramel.
• a hop containing beverage will typically contain at least 0.5 mg kg preferably at least 1 mg/kg, more preferably at least 3 mg/kg and most preferably at least 10 mg/kg of the pyrazine derivatives as defined herein before.
• the hop containing beverage contains at least 0.5 mg/kg, preferably at least 1 mg/kg of a fructosazine selected from the group consisting of 2,5- deoxyfructosazine, 2,6-deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• a fructosazine selected from the group consisting of 2,5- deoxyfructosazine, 2,6-deoxyfructosazine, 2,5-fructosazine, 2,6-fructosazine and combinations thereof.
• the benefits of the present light stabilising composition will be particularly apparent in light sensitive products that have been packaged in containers that are transparent to light with a wavelength of less than 500 nm, especially less than 400 nm, e.g. green, clear and blue glass. Consequently, in a preferred embodiment, the present hop containing beverages is bottled in green, clear or blue glass, especially in clear or green glass.
• the solids content of a material is determined by drying a sample upon a carrier composed of pure quartz sand that passes a No. 40 but not a No. 60 sieve and has been prepared by digestion with hydrochloric acid, washed acid-free, dried and ignited. Mix 30.0 g of prepared sand accurately weighed with 1.5-2.0 g accurately weighed material and dry to constant weight at 60°C under reduced pressure 50 mm Hg (6.7 kPa). Record the final weight of the sand plus caramel or decolourised caramel. Calculate the % solids as follows:
• W F final weight of sand plus caramel
• Colour Intensity of a certain material is defined as the absorbance of an 0.1% (w/v) solution of solids in water in a 1 cm quartz cell at 610 nm. If necessary, pH of the solution is adjusted to between 4 and 7. Procedure
• Absorbance Ratio of a material is defined as the absorbance of an 0.1% (w/v) solution of solids in water at 280 nm divided by the absorbance of the same solution at 560 nm. If necessary, pH of the solution is adjusted to between 4 and 7.
• Procedure Transfer an amount of material equivalent to 100 mg solids into a 100 mL volumetric flask with the aid of water, dilute to volume, mix and centrifuge if solution is cloudy. Pipet a 5.0 mL portion of the clear solution into a 100 mL volumetric flask, dilute to volume with water, and mix. Determine the absorbance of the 0.1 % (w/v) solution in a 1-cm cell at 560 nm and that of the 1:20 (v/v) diluted solution at 280 nm with a suitable spectrophotometer previously standardized using water as reference.
• a suitable spectrophotometer is one equipped with a monochromator to provide a bandwidth of 2 nm or less and of such quality that the stray-light characteristic is 0.5% or less.
• EBC EBC recommended method (European Brewery Convention, Analytica, 1987), whereby absorbance of light is measured at 430 nm in a 1 cm quartz cuvette, against water as the reference. The absorbance value measured is multiplied by an empirically derived factor of 25, to give a colour value in terms of EBC colour units.
• EBC A 430 x 25.
• Example 1 A light stabilizing composition according to the present invention was prepared from caramel (type D35 ex Devolder S.A.-N.V.) as follows: 20 gram liquid caramel (60-80% dry wt. solid) was dissolved in 200 mL distilled water and ultrafiltered using a Millipore Amicon® series 8000 (model 8400, 400 mL) stirred cell, equipped with a Millipore® YM10 regenerated cellulose ultrafiltration membrane (10,000 nominal molecular weight limit, diameter: 76 mm, cat. no. 13642).
• caramel type D35 ex Devolder S.A.-N.V.
• Example 2 An LC-PDA analysis was performed to identify the substances that are mainly responsible for the UV abso ⁇ tion characteristics of the light stabilising composition described in example 1.
• Example 3 The light stabilising properties of a caramel derived composition according to the invention were assessed by adding the light stabilising composition described in Example 1 to Heineken® pilsner (the Netherlands) in dosages of 0.5, 1.0 and 2.0 g/L (dry weight). The composition was added to freshly brewed beer, which was subsequently bottled in a 300 mL green glass bottle (Heineken® export, BSN or Rexam bottle 35.5 EB-5 GR). Bottling was performed in such a way that entrapment of atmospheric oxygen in the beer and headspace was minimised. The bottles containing the light stabilising composition in the indicated amounts as well as a bottle with a control sample were exposed to simulated sunlight by a Xenon lamp (Atlas Material Testing Technology).
• the light dose was 2700 KJ/m during 60 minutes.
• the samples containing 1.0 g/L of the stabilising composition were illuminated under the same conditions for 2, 8 and even 24 hrs.
• the concentration of MBT in the samples can suitably be determined by means of the method described by Hughes et al. (Hughes P. S., Burke S. and Meacham A. E. (1997) "Aspects of the lightstruck character of beer". Institute of Brewing, Proceedings of the 6th Central and South Africa Section, pp. 123-128). Analyses of the aforementioned samples showed that the MBT concentration in the samples containing the light stabilising composition was significantly lower than the MBT concentration found in the control sample.
• the above graph also shows that the effectiveness of the present light stabilising composition increases with increasing exposure to light (see % reduction of 1.0 g/L sample as function of light exposure time).
• the effect of the stabilising composition according to Example 1 on the colour of the aforementioned beer samples was determined by measuring the EBC colour value and the A 280/560 abso ⁇ tion ratio using the method described herein before.
• the same parameters were analysed for beer samples that contained the caramel starting material (original caramel) of Example 1 instead of the treated (decolourised) caramel. The following results were obtained:
• Caramel B Caramel color No. 310 ex D.D. Williamson Caramel C: Type D35 ex Devolder S.A.-N.V.
• Example 5 The abso ⁇ tion characteristics of the light stabilising composition described in Example 1 were compared with those of the 2 constituents (2,5- and 2,6- deoxyfructosazine) that were deemed to be largely responsible for the UV-abso ⁇ tion properties of said composition around 280 nm (see Example 2) Samples were prepared as follows: An amount of material equivalent to 100 mg solids was transferred into a 100 mL volumetric flask with the aid of water, followed by dilution to volume, stirring and centrifuging if the solution is cloudy. Subsequently, a 5.0 mL portion of the clear solution is pipetted into a 100 mL volumetric flask, diluted to volume with water, and stirred.
• the absorbance of the samples thus prepared was measured in a 1-cm quartz cell at 280 nm with a suitable spectrophotometer that was previously standardized using water as reference.
• a suitable spectrophotometer is one equipped with a monochromator to provide a bandwidth of 2 nm or less and of such quality that the stray-light characteristic is 0.5% or less.
• the abso ⁇ tion curves for 2,6-deoxyfructosazine, 2,5-deoxyfructosazine and decolourised caramel samples were determined as follows. The spectra were normalised on the highest abso ⁇ tion in the 250-300 nm area (figures). From the results obtained in Example 2 and the UV abso ⁇ tion data it can be calculated that the aforementioned deoxyfructosazines account for about 40% of the UV abso ⁇ tion at 280 nm in this specific decolourised caramel.
• Example 6 Milk is known to develop undesirable flavour changes when it is exposed to light, in particular sunlight. As a result of such exposure milk lipid oxidation products such as pentanal and hexanal, and dimethylsulphide are formed. Experiments were conducted to determine the effect of light stabilising compositions according to the invention on light induced off-flavour development in milk. Three 14 mL milk samples were prepared in duplicate in 20 mL SPME (solid phase micro-extraction) vials (flat bottom (23mm x 75mm) headspace vial with PTFE lined silicone closure (cat. no. 27199 and 27300) ex Supelco®) in a glove box under a carbon dioxide atmosphere and sealed tight.
• SPME solid phase micro-extraction
• Samples A and C Milk without addition
• Sample B Milk containing 1 g/L of the light stabilising composition described in Example 1.
• Samples A were wrapped in aluminium foil and placed in a sunbox together with the other samples and illuminated for 30 minutes with the Xenon lamp used in Example 3. The light dose applied was 1350 kJ/m .
• the samples were analysed by SPME-GC-MS. The results obtained show that all the milk samples contain dimethylsulfide.
• the dimethylsulfide concentration had been reduced after illumination in comparison to samples A and a significant increase was observed in the concentration of dimethyldisulfide.
• the observed increase in dimethyldisulfide content of sample C was considerably higher than that of sample B.
• Dimethyldisulfide is a particularly foul smelling substance with an extremely high odour potency.
• Example 7 Experiments were carried out to determine the light stabilising properties of fructosazines in beer.
• the samples were prepared by 1:1 (v/v) dilution of the fermented decolourised caramel with acetonitrile followed by filtration (PVDF 0.45 ⁇ M syringe filters) prior to analysis.
• Fractions collected were subjected to solvent evaporation (rotary evaporator) and freeze-drying, yielding a 7,5% fraction containing 2,6-deoxyfructosazine and a 4% fraction containing 2,5- deoxyfructosazine.
• the isolated fractions contained only very minor concentrations of contaminants. Both isolates were dosed to Heineken® beer at 250 mg/L in clear glass vials and illuminated for 12 min. It was found that both products reduced MBT formation by about 60%.
• Example 8 Cation Exchange material (Sigma-Aldrich, Dowex ® 50WX4-400 strong cation exchange) was brought into the IT 1" form with a IM aqueous HCl solution and thoroughly washed with distilled water until the washings were neutral.
• the EBC colour value of the beer samples was determined as well as the reduction in MBT content versus the control sample, using the MBT analysis described in Example 3. The results obtained are presented in the following graphs.

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