EA044098B1 - METHOD FOR PRODUCING CHOCOLATE WITH ANTIOXIDANTS - Google Patents

Description

Field of technology to which the invention relates

The invention relates to the food industry, namely to the technology for producing chocolate with antioxidants.

Prior Art

A recipe for chocolate obtained from cocoa mass and sugar is known from the prior art (Jeff Talbot Technology of glazed products and products with fillings, St. Petersburg: Profession, 2011 - 496 pp. (p. 63, table 3.9, volume Dark chocolate for bars) ).

The technology of processing cocoa beans from the moment of collection and fermentation to processing into semi-finished cocoa products with subsequent production of chocolate is widely known (A.V. Zubchenko Technology of confectionery production, VGTA, Voronezh, 1999 (Textbooks and teaching aids for students of higher educational institutions), 432 pp. . (p.14-97)).

However, these sources do not mention the benefits of natural substances - catechins contained in cocoa beans, and possible ways to preserve them.

Catechins are natural substances found in plants, especially tea plants, grapevines, and cocoa beans. Catechins are colorless crystals with an astringent taste, dissolve well in water, methanol and ethanol, and turn green with an alcoholic solution of ferric chloride. Catechins belong to the flavone group. The catechin molecule contains two asymmetric carbon atoms; For each catechin, 4 optically active isomers and 2 racemates are known. Catechins can be separated and extracted with wet diethyl ether or a mixture of ethyl acetate and carbon tetrachloride. Catechins are obtained from plant materials; synthesis is possible. They are biologically highly active substances, they regulate the permeability of blood capillaries and increase the elasticity of their walls, promoting better absorption of ascorbic acid by organisms.

Cocoa contains monomeric primary polyphenols (isomers (-)epicatechin and (+)epicatechin), as well as oligomeric and polymeric flavonols. The most common flavonol found in cocoa is epicatechin. It is quickly absorbed and is detected in the blood plasma within 30 minutes after consumption.

After 2-3 hours, the level of epicatechin reaches its maximum value and shows a strong positive correlation with the amount of chocolate eaten. Experimental data have shown that monomeric ((-)epicatechin and (+)epicatechin) and dimeric flavonols reduce NF-jB activation, thus leading to a decrease in oxidative stress and IL2 synthesis. There is also good evidence that cocoa flavonols protect LDL from oxidation.

Thus, consumption of cocoa and products containing it has a beneficial effect on health due to the vasodilating, antioxidant and anti-inflammatory effects of these compounds.

The problem remains that the scientific evidence supporting the beneficial effects of epicatechins in cocoa is based on large amounts, equivalent to at least 80-100g of dark chocolate, daily. Thus, it is necessary to retain as much of the original cocoa catechins during processing as possible, allowing for the consumption of small amounts of chocolate while still achieving the significant beneficial effects of cocoa epicatechins.

In the prior art, various methods are known for preserving the original catechins during the processing of cocoa beans and other chocolate semi-finished products.

For example, US Pat. No. 6,737,088 B1, May 18, 2004, discloses a method for processing cocoa beans that preserves beneficial flavonoid compounds from the cocoa beans in the final cocoa bean-based food product. This method avoids the significant losses of polyphenols that occur during conventional cocoa processing by removing a significant amount of said polyphenols prior to fermentation and/or roasting and then adding back a portion of these polyphenols.

In patent EA 16229 B1, 03/30/2012, the preservation and/or increase in the antioxidant activity of the dark chocolate mass is achieved through selected conching modes of the chocolate mass.

From the publication Clinical studies of Esthechoc beauty chocolate obtained using Astacelle technology, J.: Les novelles esthetiques, 2/2018 Astacelle technology is known to increase the bioavailability of carotenoids and epicatechins by introducing astaxanthin, obtained from the green microalgae Haematococcus pluvialis, into the chocolate mass. The technology takes advantage of the fact that astaxanthin is not subject to enzymatic breakdown in the gastrointestinal tract, due to which the substances included in astaxanthin micelles (Astacelles) are protected from oxidation by gastric juice or from modification by intestinal enzymes.

Astaxanthin is a carotenoid, a red, fat-soluble pigment extracted from the algae Hematococcus pluvalius. As a powerful antioxidant, astaxanthin protects cell membranes of all organs. Unlike beta-carotene, vitamin C and other antioxidants, which are located either inside or outside the lipid membrane, astaxanthin molecules have the unique ability to be both inside and outside the lipid membrane. This provides additional comprehensive cell protection. Astaxanthin is approved for use as a food additive in the countries of the customs union as a raw material for the production of biologically active food additives.

- 1 044098

Used in the cosmetics industry, it is also used as an ingredient in sports nutrition and food fortification.

From patent US 10849336 B2, 12/01/2020, a method is known for producing chocolate containing astaxanthin in an amount of 0.1 to 1 mg per 1 g of chocolate, chosen by the applicant as the closest analogue.

However, if during the processing of cocoa beans and chocolate semi-finished products the amount of natural catechins is greatly reduced, the use of Astacelle technology will be ineffective.

Disclosure of the Invention

Thus, the technical problem to which the present invention is aimed is the development of a technology for the production of chocolate with a high content of natural antioxidants from cocoa catechins and their optimal bioavailability for the human body.

The technical result consists in creating a technology that ensures the preservation of natural catechins from cocoa beans during processing with their subsequent encapsulation in astaxanthin premicelles.

The objective is achieved by the fact that the method for producing chocolate involves sending cocoa beans of the Criollo and/or Trinitario variety for fermentation by placing cocoa beans with pulp in boxes no later than 6-8 hours after separating the pulp from the skin of the fruit; during the first day the temperature is maintained at no more than 30°C, on the second and third days the temperature is maintained at no more than 40°C, on the fourth and fifth days the temperature is maintained at 45°C, on the sixth day natural centralized drying is carried out, fermented cocoa beans are roasted in a hot air stream at 115°C until their humidity is reduced to 2%, sharply cooled to 35°C and crushed while simultaneously separating the husk to obtain cocoa nibs, then grind cocoa nibs on melangeurs with a low temperature regime at a temperature of 40°C for 48 hours to obtain cocoa grated, the resulting cocoa mass is mixed with coconut sugar at the ratio: cocoa mass - 85-100 wt.%; coconut sugar 0-15 wt.%, the resulting mixture is crushed on a roller unit to a particle size of 35 microns without additional heating to obtain a pre-crushed chocolate mass, to which crushed astaxanthin obtained from the green microalgae Haematococcus pluvialis is added, in the ratio pre-crushed chocolate mass - 5 g: astaxanthin - 3.5 mg, the resulting mass is sent for conching in melanger at a temperature of 45 ° C for 24 hours, then the chocolate mass is tempered at a temperature drop to 32 ° C, the chocolate mass is molded into molds and cooled to a temperature of 4 ° WITH.

The premium cocoa beans used, Criollo and/or Trinitario varieties, are characterized by the following parameters. Growing regions: the island of Ceylon, Java, the northern coast of South America, Caracas, Ecuador. The length of cocoa beans is 28-30 mm, the weight of one cocoa bean is at least 2.5 g. The cocoa beans are large, sorted, round in shape, the husk is red-brown, the taste and aroma are pronounced. High-grade cocoa beans have flavor and aromatic properties that do not require the addition of additional ingredients in the form of flavoring agents.

Chemical composition of commercial cocoa beans,%:

core 85-89;

husk 10-14;

germ to 1;

fats 48-54;

humidity 4-6;

starch up to 15;

proteins 11-15;

sugars about 12 (mainly glucose);

fiber up to 21;

organic acids 12 (mainly acetic, formic acids);

caffeine up to 0.5.

The use of the specified cocoa beans with specified fermentation and drying protocols on the plantation by the farmer at specified temperature intervals makes it possible to obtain the chemical composition of seeds with unique flavor precursors and a high content of catechins.

When roasting cocoa beans, due to the mechanical removal of moisture, the acidity is reduced from 13 to 11% (volatile and partially bound acids), the content of tannins is reduced from 6 to 5%, and humidity from 6 to 2%. An inversion of sucrose occurs, a reaction of melanoid formation occurs, as a result of which the cocoa beans acquire a certain taste and aroma, become fragile, and the cocoa shell (husk) begins to separate.

The lower the humidity, the better the cocoa beans are crushed into cocoa nibs, which subsequently makes it possible to obtain a larger amount of cocoa butter from cocoa liquor. But the humidity should not be lower than 2%. Due to their increased hygroscopicity, cocoa beans are not stored, but are immediately sent for processing.

- 2 044098

A gentle method of frying in a fluidized bed of hot air is used to fix the isolated precursors at the time of fermentation and form the final aromatic compounds, such as aspartic acid at the rate of 27 mg per 100 g, glycine 5 mg/100, lysine 23 mg per 100 g.

Breeze ovens are used as roasting equipment. The temperature regime in Breeze ovens is used to obtain the temperature of the cocoa bean product in increments of 7-8°C, namely: air temperature 115°C, cocoa bean temperature 108-107°C. The method is not applicable if fermentation protocols have been violated. Frying methods on Breeze equipment are selected to reveal the precursors obtained during fermentation.

After roasting the cocoa beans, they are sharply cooled to a temperature of 35°C.

In the process of grinding roasted cocoa beans into cocoa nibs and then obtaining cocoa liquor, low-temperature conditions are selected. The cocoa bean kernel has a cellular structure containing cocoa butter; during the grinding process, the cell walls are destroyed, heat from friction melts the cocoa butter, the size of the non-fat particles decreases and the mixture gradually becomes fluid and viscous in cocoa nibs. Grinding on low-temperature grinders does not destroy the beneficial properties of fermented, roasted cocoa beans, but preserves their functionality.

Grinding occurs in a millstone mill (melanger), the degree of grinding and additional evaporation of acids occur simultaneously, which improves the properties of cocoa liquor. In general, grinding occurs within 48 hours.

Next, prepare the chocolate mass as follows. Coconut sugar is added to the cocoa mass, grinding the mass to 35 microns without additional heating. The choice of a chocolate recipe based only on cocoa mass and coconut sugar in the specified proportions ensures the maximum content of catechins in a portion of the product and the consumer organoleptic properties of the product. There is no need to add cocoa butter to the chocolate mass recipe, since the resulting cocoa mass provides all the necessary rheological properties of the mass required for molding. In addition, standard cocoa butter extraction technology leads to the destruction of polyphenols due to high pressure, and the inclusion of such a component in the recipe of this chocolate is undesirable.

At the final stage, crushed astaxanthin is added to the chocolate mass in a proportion of 3.5 mg per 5 g, followed by transfer of the chocolate mass to a mill with a thermal jacket, where additional slow conching occurs at a temperature of 45 ° C.

When tempering chocolate, cocoa butter crystallizes when the temperature drops to 32°C and epicatechin is immediately enclosed in astacanthin micelles. After which the chocolate mass is sent for molding into molds and cooled to 4°C.

Thus, during the process of fermentation, roasting and grinding on melangeurs, the required chemical composition of flavoring and aromatic precursors in chocolate is achieved by selecting the specified operating parameters (temperature, time, degree of grinding, final humidity). It has been experimentally established that the specified parameters of the fermentation, roasting and grinding processes on melangeurs provide maximum release and increased content of isoflavanols of such epicatechins in the finished product in comparison with known products obtained through standard known stages of fermentation, roasting and grinding of cocoa nibs into cocoa liquor.

When tempered, epicatechins and astaxanthin are then bound into premicelles, which ensures maximum absorption into the lymphatic system and minimizes their metabolism in the liver, as well as breakdown in the gastrointestinal tract. The described astaxanthin crystallization technology increases the bioavailability of carotenoids and epicatechins by creating premicelles that act as bodyguards and promote the incorporation of substances into mixed lipid micelles in the gastrointestinal tract. Co-crystallization of cocoa epicatechins in astaxanthin micelles during the tempering process produces protected crystals of epicatechin in high concentrations, not present in regular chocolate. As a result of the use of the proposed technology, the delivery of substances in unchanged form to the site of absorption in the intestine increases. Chocolate can not only effectively inhibit markers of inflammation and oxidative stress, but also improve age-related changes in oxygenation of peripheral tissues, including the skin.

The clinical effectiveness of chocolate was more pronounced compared to consuming the same amounts of its constituent components separately.

Examples

Example 1.

Cocoa beans of the Criollo variety are sent for fermentation by placing cocoa beans with pulp in boxes 8 hours after separating the pulp from the skin of the fruit. During the first day, the temperature is maintained at no more than 30°C; on the second and third days, the temperature is maintained at no more than 40°C. On the fourth and fifth days, the temperature is maintained at 45°C; on the sixth day, natural centralized drying is carried out. Fermented cocoa beans are roasted in a hot air stream at a temperature of 115°C until their moisture content is reduced to 2%, sharply cooled to 35°C and crushed while simultaneously separating the husk to obtain cocoa nibs. Afterwards they carry out

- 3 044098 grinding cocoa nibs on melangeurs with low temperature conditions at a temperature of 40°C for 48 hours to obtain cocoa liquor. The resulting cocoa mass is mixed with coconut sugar in the following proportions: cocoa mass - 85 wt.%; coconut sugar - 15 wt.%. The resulting mixture is crushed on a roller unit to a particle size of 35 microns without additional heating to obtain a pre-crushed chocolate mass. Crushed astaxanthin, obtained from the green microalgae Haematococcus pluvialis, is added to the mass in the ratio of pre-crushed chocolate mass 5 g: astaxanthin 3.5 mg. The resulting mass is conched in melangere at a temperature of 45°C for 24 hours, then the chocolate mass is tempered when the temperature drops to 32°C, and crystallization of cocoa butter occurs and the simultaneous encapsulation of epicatechin in astaxanthin micelles. Then the chocolate mass is poured into molds and cooled to a temperature of 4°C, followed by packaging.

Example 2.

Trinitario cocoa beans are sent for fermentation by placing cocoa beans with pulp in boxes 4 hours after separating the pulp from the skin of the fruit. Next, repeat the operations according to example 1, at the stage of mixing cocoa liquor and coconut sugar, take cocoa liquor in an amount of 90 wt.%; coconut sugar - 10 wt.%.

Example 3.

Cocoa beans of the Criollo and Trinitario varieties, taken in a mass ratio of 1:1, are sent for fermentation by placing cocoa beans with pulp in boxes 6 hours after separating the pulp from the skin of the fruit. Next, repeat the operations according to example 1, at the stage of mixing cocoa liquor and coconut sugar, take cocoa liquor in an amount of 88 wt.%; coconut sugar - 12 wt.%.

Example 4.

Cocoa beans of the Criollo variety are sent for fermentation by placing cocoa beans with pulp in boxes 7 hours after separating the pulp from the skin of the fruit. During the first day, the temperature is maintained at no more than 30°C; on the second and third days, the temperature is maintained at no more than 40°C. On the fourth and fifth days, the temperature is maintained at 45 °C; on the sixth day, natural centralized drying is carried out. Fermented cocoa beans are roasted in a hot air stream at a temperature of 115°C until their moisture content is reduced to 2%, sharply cooled to 35°C and crushed while simultaneously separating the husk to obtain cocoa nibs. Afterwards, cocoa nibs are ground on melangeurers with a low temperature regime at a temperature of 40°C for 48 hours to obtain cocoa liquor. Use 100 wt.% cocoa liquor. Next, grinding is carried out on roller units to a particle size of 35 microns without additional heating to obtain a pre-crushed chocolate mass. Crushed astaxanthin, obtained from the green microalgae Haematococcus pluvialis, is added to the mass in the ratio of pre-crushed chocolate mass 5 g: astaxanthin 3.5 mg. The resulting mass is conched in melangere at a temperature of 45°C for 24 hours, then the chocolate mass is tempered when the temperature drops to 32°C, and crystallization of cocoa butter occurs and the simultaneous encapsulation of epicatechin in astaxanthin micelles. Then the chocolate mass is poured into molds and cooled to a temperature of 4°C, followed by packaging.

The resulting chocolate according to examples 1-4 is characterized by organoleptic properties and physicochemical characteristics given in table. 1.

Table 1

Indicator name Suggested method Taste and smell Intense chocolate aroma, pleasant aftertaste, no cloying, sour or bitter aftertaste Consistency Solid Appearance The front surface is smooth and shiny Structure Homogeneous Antioxidant content according to HPLC data, mg per 5 g of product Astaxanthin, mg 3.5 Epicatechins, µg/g 216

During a tasting assessment of the resulting chocolate, it was found that the chocolate bars do not contain traces of blooming, the surface of the bars is smooth and shiny. Chocolate has a dense texture, is easy to bite and does not have any unpleasant aftertaste when chewed. The energy value (calorie content) of chocolate was 560 kcal. per 100 g. Glycemic index - from 22 to 36 units.

Confirmation of the development of a technology for the production of chocolate with a high content of natural antioxidants from cocoa catechins was obtained during a comparative analysis of chocolate obtained using the closest analogue of US 10849336 B2, 12/01/2020, and chocolate obtained using the declared technology. Content of catechin and epicatechin in chocolate (Table 2).

table 2

Indicators In cocoa beans, the variety is criollo/trinitario fermented The closest analogue Declared chocolate Total catechin, mcg/g 1200 214 280 Epicatechin, mcg/g 2800 179 216

Thus, from the above, including from the table presented, it follows that the developed method for producing chocolate made it possible to obtain chocolate with a high content of natural antioxidants from cocoa catechins.

Confirmation of the effectiveness and bioavailability of catechins and epicatechins when using chocolate was obtained in the course of a study. All patients participated in the study voluntarily and signed a voluntary informed consent form. The volunteers were divided into two groups: the experimental group took chocolate obtained using the stated technology, and the control group took chocolate according to the closest analogue of US 10849336 B2, 12/01/2020. For 21 days, volunteers (experimental and control groups) consumed 5 g of chocolate per day. The dynamics of the total concentration of epicatechin in the serum of patients, obtained during a cross-over study, obtained before taking chocolate and 21 days after drinking 5 g of chocolate for each day. Measurements were carried out 1 hour after taking the last portion of chocolate (Table 3).

Table 3

Indicators The closest analogue Declared chocolate serum epicatechin concentrations, mcg/ml: before appointment after 21 days 0 0.7 0 0.79

Thus, after taking chocolate obtained by the claimed method, the total concentration of epicatechin in the blood serum increased compared to the closest analogue.

The finished product meets all safety requirements, has biological value, is distinguished by high organoleptic characteristics, structural-mechanical and physicochemical quality indicators of chocolate meet the requirements of regulatory documents.

-

Claims (2)

CLAIM 1. A method for producing chocolate, characterized by the fact that cocoa beans of the Criollo and/or Trinitarian varieties are sent for fermentation by placing cocoa beans with pulp in boxes no later than 6-8 hours after separating the pulp from the skin of the fruit, during the first day the temperature is maintained at no more than 30°C, on the second and third days the temperature is maintained at no more than 40°C, on the fourth and fifth days the temperature is maintained at 45°C, on the sixth day natural centralized drying is carried out, fermented cocoa beans are roasted in a hot air stream at 115°C until their humidity is reduced to 2%, sharply cooled to 35°C and crushed while simultaneously separating the husk to obtain cocoa nibs, then grind cocoa nibs on melangeurs with a low temperature regime at a temperature of 40°C for 48 hours to obtain cocoa grated, then grinded on roller units to a particle size of 35 microns without additional heating to obtain a pre-crushed chocolate mass, to which crushed astaxanthin obtained from the green microalgae Haematococcus pluvialis is added, in the ratio pre-crushed chocolate mass - 5 g: astaxanthin - 3.5 mg, the resulting mass is sent for conching in a melangeur at a temperature of 45°C for 24 hours, then the chocolate mass is tempered by lowering the temperature to 32°C, the chocolate mass is formed into molds and cooled to a temperature of 4°C. 2. The method according to claim 1, characterized in that additionally, before grinding on a roller unit, cocoa liquor is mixed with coconut sugar at a cocoa mass ratio of 85-100 wt.%; coconut sugar 0-15 wt.%. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky lane, 2