Gluten-free extract and brown color containing it

Abstract

Extract of at least one malted cereal, preferably a gluten-free cereal, particularly preferably maize, produced by a process comprising the following steps: a) Milling of at least one roasted, malted grain, preferably a gluten-free grain, particularly preferably maize, b) enzymatic treatment of the milled material with one or more enzymes, wherein at least one enzyme is a starch-splitting enzyme, c) Inactivation of enzymes in the material from step b), so that it is essentially free of starch, preferably inactivation by heat treatment, d) Solid-liquid separation of the material from step c). e) optional preservation of the liquid phase from step d). f) optionally one or more filtrations of the liquid phase from step d) or of the preserved product from step e), g) Concentrating the product to obtain an extract with Brix 50° - 70°, preferably 55° - 65°, wherein the content of 4-methylimidazole is less than 5 mg / kg.

Description

[0001] The invention relates to a gluten-free extract and a brown colorant containing this extract, as well as a method for coloring an orally edible preparation by using this extract as a gluten-free brown colorant, wherein the orally edible preparations are selected from foods, food supplements, stimulants, cosmetic products or pharmaceuticals.

[0002] Various substances are known for use as caramel or brown coloring agents in the food industry. For example, DE 1 954 489 discloses a caramel coloring agent used in carbonated, non-alcoholic beverages.

[0003] Brown food colorings such as caramel E150d, also known as Class IV caramel, can form undesirable byproducts such as 4-methylimidazole (4-MEI), hydroxymethylfurfural, or acrylamides due to the reaction of reducing sugars with ammonium sulfites. Roasted, malted grains obtain their brown color through a different process, namely Maillard reactions, and therefore produce significantly fewer of these byproducts.

[0004] The most well-known malted grain is certainly barley, as it is widely used in beer production. One indicator of quality is the color of the malt, which results in different beer styles, ranging in color intensity from light brown to amber to very dark beers of the "Schwarzbier" type.

[0005] Roasted and malted barley is not only used in beer production, but also as a natural brown ingredient, e.g. in the production of baked goods with a darker color such as bread or other pasta.

[0006] WO 1980002695 can be considered the closest prior art. This document describes a process for producing an edible colorant by digesting roasted malted grain in water using enzymes such as protease (e.g., papain) together with a mixture of carbohydrases (e.g., alpha-amylase and beta-glucanase). An aqueous extract is separated from the remaining solids and can be used as a brown colorant in foods and beverages. The use of maize as the grain is mentioned, along with other grains such as wheat, rye, oats, sorghum, and rice. However, in the examples, only barley is malted as the grain to obtain malted barley. This malted barley is then roasted to obtain roasted barley malt, preferably of the "black malt" type.As shown in Table 4, the final product typically has a 4-MEI content of 10 to 15 ppm (or 10 to 15 mg / kg) and a color of 16,000 to 19,000 EBC units at 80% solids content.

[0007] Malting and roasting grains is not limited to barley, however, but can be applied to all types of grain, such as wheat, rapeseed, oats, rice, etc., and also to pseudocereals like buckwheat, quinoa, amaranth, and even legumes like peas or beans. Gluten-containing grains such as wheat, barley, or rye are associated with celiac disease. Even though there are processes that can remove gluten, for example through enzymatic reactions, such products still have to be labeled as allergens, which limits their safe use in applications other than beer or baked goods, which naturally contain gluten due to the raw materials used.

[0008] It is therefore an object of the invention to find a gluten-free coloring agent for use in the food industry. A further object of the invention is to find a coloring agent that contains a low amount of undesirable byproducts such as 4-methylimidazole (4-MEI), hydroxymethylfurfural, or acrylamides.

[0009] Malted and roasted maize (Zea mays L.) is known as a snack or as a raw material for beer production and replaces some of the malted and roasted barley. However, these known malted and roasted maize products have not been used for the production of extracts that can be used as natural brown colorants. Within the scope of the present invention, it was found that these known malted and roasted maize products cannot be used for the production of natural brown ingredients due to their unsuitable color intensity.

[0010] Therefore, a further object of the invention is to find a method for producing an extract that can be used as a natural brown ingredient for coloring food.

[0011] These problems were surprisingly solved by an extract from at least one roasted, malted grain, preferably maize, produced by a process comprising the following steps: a) Milling of at least one roasted, malted grain, preferably a gluten-free grain, particularly preferably maize, b) enzymatic treatment of the milled material with one or more enzymes, wherein at least one enzyme is a starch-splitting enzyme, c) Inactivation of the enzymes in the material from step b), after it is essentially free of starch, preferably inactivation by heat treatment, d) Solid-liquid separation of the material from step (c), e) optional preservation of the liquid phase from step (d), f) optionally one or more filtrations of the liquid phase from step (d) or of the preserved product from step (e), g) Concentrating the product to obtain an extract with Brix 60 - 62°, where the content of 4-methylimidazole is less than 5 mg / kg.

[0012] Within the scope of the present invention, the term "cereals" refers to cereals, pseudocereals, and pulses. The cereals may be selected from the group comprising maize, oats, rice, wheat, rye, barley, triticale, millet, bamboo, and mixtures thereof. The pseudocereals may be selected from the group comprising buckwheat, quinoa, amaranth, canihua, and mixtures thereof. The pulses may be selected from the group comprising peas, beans, chickpeas, lentils, and mixtures thereof.

[0013] Preferably, at least one gluten-free grain is used. A mixture of at least two gluten-free grains can also be used. In a preferred embodiment of the invention, maize is used as the grain.

[0014] Within the scope of the present invention, the term "malted grain" refers to the product also known as "malt". Malt is a germinated grain kernel that is germinated by soaking in water and then prevented from further germination by drying with hot air. This process is called "malting".

[0015] Within the scope of the present invention, the term ‘roasted, malted grain’ used in step a) is a product obtained by roasting the malted grain, preferably malted corn, at a temperature of more than 170 °C, preferably between 180 °C and 210 °C, for 2 to 3 hours.

[0016] In a preferred embodiment of the invention, the roasted, malted grain used in step a) is roasted, malted corn. For example, roasted, malted corn from the company “Hitit Malt”, Turkey, can be used.

[0017] At least one starch-digesting enzyme used in step b) is selected from the group consisting of glucoamylase, alpha-amylase, beta-amylase, and pullulanase. Glucoamylase is preferably used. The use of Amylase® AG XXL is particularly preferred. The amount of enzyme is typically 200–250 mg per 1 kg of the milled material. Optionally, at least one additional enzyme that increases alpha-amylase activity, e.g., Beerzyme® Crystal, may be added. The amount of Beerzyme® Crystal is typically 200 mg per 1 kg of the milled material.

[0018] In a preferred embodiment of the invention, at least one starch-digesting enzyme can be used in combination with at least one other enzyme from the group consisting of xylanases, glucanases, and mixtures thereof. Preferably, endo-glucanases and / or xylanase are used. Ultraflo® Max is particularly preferred in the present invention. The amount of Ultraflo® Max is typically 250 mg per 1 kg of the milled grain. Extract from at least one roasted, malted grain

[0019] The extract according to the invention is the extract from at least one roasted, malted grain, preferably the extract from roasted malted maize. This extract is produced according to the process described above. The extract has a low viscosity, preferably - Viscosity 20°C 60° Brix is ​​less than 1000 mPa·s, particularly preferably between 600 and 630 mPa·s. - Viscosity 20°C65° Brix less than 4000 mPa · s, particularly preferably between 1800 and 2000 mPa · s.

[0020] The viscosity was determined using the viscometer “Brookfield LV DV-E” with s62 spindle, speed 20 rpm, 50% torque.

[0021] For the characterization of the extract according to the invention, at least one of the following parameters can also be used: Brix 50° - 70°, preferably 55° - 65°, - EBC 430nm 7500 to 11000, preferably 8000 - 10000, pH undiluted :4 - 5 and / or - NTU (1Bx) Maximum 30, preferably around 25

[0022] A liquid has a degree Brix (1° Brix) if it has the same density as a solution of 1 g of sucrose in 100 g of an aqueous sucrose solution. EBC paint

[0023] The EBC-recommended method (European Brewery Convention, Analytica, 1987) involves measuring the absorption of light at 430 nm in a 1 cm quartz cuvette against water as a reference. The measured absorption value is multiplied by an empirically derived factor of 30.8 to obtain a color value in EBC color units. EBC = A430 × 30.8. The EBC color scale is a recognized method for classifying the color of beers, malt and caramel solutions, and similarly colored liquids.

[0024] For EBC determination, a solution was prepared from demineralized water adjusted to pH 3 with citric acid. 0.2 wt% of the extract from roasted malted corn was added to this solution.

[0025] The Nephelometric Turbidity Unit (NTU) is a unit used to measure the turbidity of a liquid and is determined using a calibrated nephelometer. The nephelometer measures the light transmission through the sample. The NTU value of the test sample is compared to that of a stabilized formazin solution with a known NTU value. Standards used by practitioners can range from 0 to 1000 NTU.

[0026] To demonstrate the advantages of the roasted malted maize extract according to the invention, a roasted malted barley extract was produced for comparison. This roasted malted barley extract was prepared by water extraction of the roasted malted barley using enzymes. The enzymes used for the production of the roasted malted barley extract were selected such that a roasted malted barley extract with a Brix value comparable to that of the roasted malted maize extract according to the present invention was produced.

[0027] The roasted malted barley was processed according to the instructions in Fig. 1. The malted barley (or barley malt) is obtained by roasting it at a temperature of more than 170 °C, preferably between 180 °C and 210 °C, for 2 to 3 hours. Comparison of the viscosity of roasted malted maize extract and roasted malted barley extract

[0028] The viscosity of a concentrate is an important property that affects the processability and ease of distribution of a concentrated component in a food or beverage.

[0029] The extract according to the invention has a low viscosity. Preferably, the roasted malted maize extract according to the invention has a lower viscosity than the viscosity of extracts produced from roasted malted barley with a comparable Brix value. As already mentioned above, the particularly preferred viscosity of the extract according to the invention at 20 °C and 60° Brix is ​​between 600 and 630 mPa·s. The particularly preferred viscosity at 20 °C and 65° Brix is ​​between 1800 and 2000 mPa·s.

[0030] The viscosity was determined using the viscometer “Brookfield LV DV-E” with s62 spindle, speed 20 rpm, 50% torque.

[0031] The following table compares the viscosity of the roasted malted maize extract according to the invention and the viscosity of the roasted malted barley extract at 60° Bx and 65° Bx. Viscosity, cp@20 °C product 60° Bx 65° Bx roasted malted barley extract 1385 5700 roasted malted corn extract 612 1917

[0032] The roasted malted corn extract has a significantly lower viscosity at a comparable Bx value, which is advantageous when filling or pumping such an extract. Undesirable byproducts

[0033] Within the scope of the present invention, it was surprisingly found that, despite high roasting temperatures, the content of undesirable byproducts in the extract according to the invention is lower than the content of undesirable byproducts in barley extracts obtained at comparable roasting temperatures. The byproducts are selected from the group consisting of 4-methylimidazole (4-MEI), hydroxymethylfurfural (HMF), acrylamides, and mixtures thereof.

[0034] The HMF content of the extract according to the invention is less than 500 mg / kg. The 4-MEI content in the extract according to the invention is less than 5 mg / kg, preferably less than 1 mg / kg, and particularly preferably less than 0.5 mg / kg. The acrylamide content in the extract according to the invention is less than 10 mg / kg.

[0035] It is known that cereals such as barley, rapeseed, or wheat contain fructooligosaccharides and soluble hemicelluloses, which are hydrolyzed during the roasting process. These hydrolysis products, namely fructose, xylose, arabinose, and glucuronic acid, are significantly more reactive than the maltooligosaccharides derived from starch hydrolysis and can generate larger quantities of these undesirable byproducts. This study examines the positive effect of processing roasted malted corn extract compared to roasted malted barley extract (see table below). roasted malted barley extract roasted malted corn extract 4-MEI 2.9 mg / kg 0.38 mg / kg HMF 919 mg / kg 172 mg / kg Acrylamide less than 10 mg / kg less than 10 mg / kg

[0036] A further object of the present invention is a coloring agent that contains or consists of the extract according to the invention. The coloring agent is a gluten-free coloring agent, preferably a gluten-free brown coloring agent.

[0037] A further object of the present invention is an orally consumable preparation containing at least one extract or at least one colorant according to the invention. The orally consumable preparations are selected from foods, food supplements, stimulants, cosmetic products, or pharmaceuticals. The amount of at least one extract is at least about 0.1% by weight, preferably about 0.1% to about 5% by weight, based on the total weight of the preparation.

[0038] A further object of the present invention is a method for coloring an orally consumable preparation by using at least one extract or at least one colorant according to the invention. The orally consumable preparations are selected from foods, food supplements, stimulants, cosmetic products, or pharmaceuticals.

[0039] The invention will be explained with reference to the accompanying examples and figures, without, however, being limited to the specifically described embodiment. The invention also relates to all combinations of preferred embodiments, provided these are not mutually exclusive. The terms "approximately" or "about" in conjunction with a numerical value mean that values ​​at least 10% higher or lower, or 5% higher or lower, and in any case values ​​1% higher or lower, are included. Fig. Figure 1: Flowchart shows the process for producing a roasted, malted, gluten-free grain, preferably maize, which is used in step a) in a preferred embodiment of the invention. Fig.2: Flowchart shows the process according to the invention for producing an extract from roasted, malted, gluten-free grain, preferably maize, in a preferred embodiment of the invention (steps ac). Fig. Figure 3: Flowchart shows the process according to the invention for producing an extract from roasted, malted, gluten-free grain, preferably maize, in a preferred embodiment of the invention (steps dg). The steps marked with the dashed line represent optional steps. Fig. 4: Photos of the cookies with different amounts of roasted, malted corn extract. Fig. 5: Photos of the muffins with different amounts of roasted, malted corn extract. Fig. 6: Photos of the solution containing 0.2 wt% of roasted malted maize extract compared to the solution containing 0.2 wt% of roasted malted barley extract. Example of the production of roasted, malted grain

[0040] As in Fig. As shown in Figure 1, the process for producing roasted, malted corn extract comprises the steps indicated. The kernels of at least one grain are sieved and then soaked in water for approximately 48 hours.

[0041] After soaking, the germination step follows. For this purpose, the softened malt obtained during soaking is kept at a temperature between 20 °C and 30 °C, for up to 4 days in the embodiment shown in the example. The green malt obtained after germination is kilned for 48 hours at a temperature between 50 °C and 100 °C. The malted grain is then roasted at a temperature above 170 °C, preferably between 180 °C and 210 °C, for 2-3 hours. The roasted malted grain, preferably corn, is then cooled to ambient temperature. The resulting roasted, malted grain, preferably roasted, malted corn, can be packaged and stored. Example of the production of the extract from roasted, malted corn according to the invention

[0042] 1325 kg of roasted, malted corn (supplier "Hitit Malt", Turkey) was milled on a hammer mill (SIMCO) at a mill speed of 1487 rpm and a screen size of 7 mm. The yield of the milled product was 1300 kg of milled material with the following particle sizes: >1 mm 35%, >0.5 mm 30%, >0.150 mm 25%, <0.150 mm 10%.

[0043] As in Fig.As shown in Figure 2, the process for producing an extract comprises the following steps. The milled material obtained in step a) is mixed with water and one or more enzymes for enzymatic treatment in step b). In the illustrated example, the mixture obtained in step b) is held at a temperature of approximately 50 °C for 40 minutes, then at approximately 65 °C for 40 minutes, and finally at approximately 75 °C for 20 minutes. At least one enzyme used in step b) is a starch-digesting enzyme, e.g., Amylase® AG XXL. Optionally, at least one further enzyme that increases amylase activity, e.g., Beerzyme® Crystal, can be added. In a preferred embodiment of the invention, at least one starch-digesting enzyme can be used in combination with at least one further enzyme from the group consisting of xylanases, glucanases, and mixtures thereof; e.g., Ultraflo® Max can be used in the invention.The enzymatic treatment in step b) is particularly preferred, using a combination of three enzymes such as Amylase® AG XXL, Beerzyme® Crystal, and Ultraflo® Max. The typical amount of Amylase® AG XXL is 250 mg per 1 kg of the milled material. The amount of Beerzyme® Crystal is typically 200 mg per 1 kg of the milled material. The amount of Ultraflo® Max is typically 250 mg per 1 kg of the milled material.

[0044] The result of enzymatic treatment b) is a largely starch-free slurry. If the starch test (also called the iodine-starch test) is still positive, the slurry can be kept at rest temperature for another 10 minutes. If the starch test shows that no starch is detectable within the usual tolerances, the enzyme inactivation step c) follows the enzymatic treatment step b) using any known method, e.g., heat treatment at a temperature of approximately 80 °C for approximately 5 to 10 minutes.

[0045] As in Fig.As shown in Figure 3, after enzyme inactivation in step c), step d) of the solid-liquid separation is carried out, during which water may be added. The ratio of added water to the spent grain obtained after step c) is 2:1. The temperature of the added water can be between 50 °C and 55 °C. Separation step d) can be carried out using any method known to those skilled in the art, e.g., decanting, filtration, sieving, pressing, settling, etc. A decanting centrifuge is preferably used.

[0046] The preservation of the liquid phase from step d) can be carried out in step e). Various methods known to those skilled in the art can be used for this purpose, e.g., pasteurization, sterilization and UV treatment, or the addition of preservatives. In this example, the liquid phase from step d) is boiled at a temperature of approximately 80–100 °C for 10–40 minutes for pasteurization.

[0047] Optionally, after boiling, the hot wort undergoes a gentle whirlpool effect, causing unwanted solids to settle in the center of the vessel. This contributes to the clarification of the wort. The sedimented portion is then drained off. After the whirlpool, the wort cools to below 35°C to prepare it for the clarification step.

[0048] Optionally, one or more filtrations can be carried out in step f) of the liquid (optionally pasteurized) phase. Any method known to those skilled in the art can be used for this filtration step f). Preferably, the filtration can be carried out with diatomaceous earth, rotating vacuum filters (also called drum filters), and / or sheet filters. For example, Becosorb® 2500 can be used for diatomaceous earth filtration. Pall Seitz® K Series Depth Filter Sheets (the pore size of the filter sheets is 20 microns, 10 microns, and 2 microns) can, for example, be used as sheet filters for filtration.

[0049] The liquid phase from solid-liquid separation step d), which may optionally be pasteurized in step e) and / or filtered in step f), is subjected to concentration step g). For the concentration according to step f), a falling film evaporator may be used, for example. The concentration is carried out to obtain the product at 55–65° Brix, preferably 60–62° Brix, for storage, transport, and use in orally consumable preparations. Turbidity stability test

[0050] The extract according to the invention exhibits high turbidity stability after pasteurization.

[0051] For measuring turbidity, three acidified and sugar-containing solutions with pH 3 are prepared. The sugar content in the first drinks is 0% by weight, the sugar content in the second drinks is 7% by weight, and the sugar content in the third drinks is 15% by weight. The dosage of the extract according to the invention is 2 g / l for each drink.

[0052] Turbidity data is given in the unit "NTU". This "Nephelometric Turbidity Unit" (NTU) is a unit for measuring the turbidity of a liquid and is determined using a calibrated Hach TL2300 EPA nephelometer.

[0053] The table below shows the results of the turbidity measurements before and after pasteurization of the extract according to the invention. Sugar content Pre-Pastor (NTU) According to Past (NTU) 0% 5,68 5,24 7% 6,36 5,09 15% 5,97 5,34

[0054] The extract according to the invention showed no increase in turbidity after pasteurization, as measured with a nephelometer (Hach TL2300 EPA), which proves its stability at a pH value typical for carbonated beverages. Preparation of baked goods (testing of thermal stability)

[0055] To demonstrate the baking stability of the extract according to the invention, baked goods such as cookies and muffins were used. The amount of at least one extract according to the invention is at least about 0.1 wt.%, preferably about 0.1 to about 5 wt.%, based on the total weight of the mixture used for baked goods.

[0056] The list of ingredients used to make the cookies is shown in the table below. Roasted malted corn extract is added to the ingredient mixture. Baking conditions: 170-180 °C (340-350 °F) top and bottom heat for 10 minutes. Ingredients Crowd % wheat flour 45,8 butter 31,8 Sugar 11,5 glucose syrup 5,1 Whole egg 5,1 baking powder 0,6 Salt 0,1

[0057] The list of ingredients used for the muffins is shown in the table below. Roasted malted corn extract is added to the ingredient mixture. Baking conditions: 170-180 °C (340-350 °F) top and bottom heat for 10 minutes. Ingredients Crowd % wheat flour 30,5 Sunflower oil 9,5 Sugar 22,8 Milk 19,0 Whole egg 17,1 baking powder 1,0 Vanillin 0,1

[0058] Fig. Figure 4 shows photos of the prepared cookies. The amount of added roasted, malted corn extract is 0.6%, 1.2%, and 2.4% by weight, based on the total weight of the ingredient mixture.

[0059] Fig. Figure 5 shows photos of the prepared muffins. The amount of added roasted, malted corn extract is 1% and 2.4% by weight, based on the total weight of the ingredient mixture.

[0060] As shown in the attached photos of Fig. 4 and Fig. As can be clearly seen in section 5, the color intensity of the products increased in parallel with the dosage of the extract, which proves its thermal stability. Testing the coloring properties of the extract in the liquid products

[0061] The color of roasted malted corn extract was compared to that of roasted malted barley extract. For this purpose, two solutions of demineralized water adjusted to pH 3 with citric acid were prepared. 0.2 wt% of the roasted malted barley extract was added to the first solution. 0.2 wt% of the roasted malted corn extract was added to the second solution. The color was measured (Hunter Lab ColorFlex EZ). The L*a*b* values ​​for the two products are shown in the table below and in Fig. 6 shown. liquid product EBC L a b Δ E with roasted malted barley extract 8900 43,70 10,72 43,54 with roasted malted corn extract 8400 42,02 10,55 41,09 2,9 QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] DE 1 954 489

[0002] WO 1980002695

[0006]

Claims

[1] Extract of at least one malted cereal, preferably a gluten-free cereal, particularly preferably maize, produced by a process comprising the following steps: a) Milling of at least one roasted, malted grain, preferably a gluten-free grain, particularly preferably maize, b) enzymatic treatment of the milled material with one or more enzymes, wherein at least one enzyme is a starch-splitting enzyme, c) Inactivation of enzymes in the material from step b), so that it is essentially free of starch, preferably inactivation by heat treatment, d) Solid-liquid separation of the material from step c). e) optional preservation of the liquid phase from step d). f) optionally one or more filtrations of the liquid phase from step d) or of the preserved product from step e), g) Concentrating the product to obtain an extract with Brix 50° - 70°, preferably 55° - 65°, wherein the content of 4-methylimidazole is less than 5 mg / kg. [2] The extract according to claim 1, characterized by that the roasted, malted grain is produced by roasting the malted grain at a temperature of more than 170 °C, preferably between 180 °C and 210 °C, for 2 - 3 hours. [3] The extract according to claim 1 or 2, characterized by that the starch-splitting enzyme is selected from the group consisting of glucoamylase, alpha-amylase, beta-amylase and pullulanase, wherein this starch-splitting enzyme is used in combination with at least one other enzyme selected from the group consisting of xylanase, glucanase and their mixture. [4] The extract according to any one of claims 1 to 3, characterized by, that the content of undesirable by-products in the extract is lower than the content of undesirable by-products in the extracts from barley obtained at comparable roasting temperatures, the by-products being selected from the group consisting of 4-methylimidazole (4-MEI), hydroxymethylfurfural (HMF), acrylamides and mixtures thereof. [5] The extract according to any one of claims 1 to 4, characterized by , that, - the HMF content is less than 500 mg / kg, - the 4-MEI content is less than 1 mg / kg and - the acrylamide content is less than 10 mg / kg. [6] The extract according to any one of claims 1 to 5, characterized by that the extract has a low viscosity, preferably - Viscosity 20°c 60° Brix is ​​less than 1000 mPa·s, particularly preferably between 600 and 630 mPa·s. - Viscosity 20°C65° Brix less than 4000 mPa · s, particularly preferably between 1800 and 2000 mPa · s. [7] Colouring agent containing or consisting of the extract according to any one of claims 1 to 6. [8] Colouring agent according to claim 7, characterized by that the colouring agent is a gluten-free colouring agent, preferably a gluten-free brown colouring agent. [9] Orally consumable preparation containing at least one extract according to any one of claims 1 to 6 or at least one colouring agent according to claim 7 or 8.

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