RU2294114C2 - Food supplement from vinasse, uses of combination of antioxidant complexes from vinasse with bioavailability promoters and method for production of food supplement - Google Patents

Abstract

FIELD: food processing industry, in particular antioxidant complexes obtained from vinasse.

SUBSTANCE: food supplement for oral administration contains particular antioxidant complexes obtained from vinasse in combination with one or more bioavailability promoters selected from group comprising polysaccharides and amino acids. Disclosed is uses of said complexes in production of food supplement with sustained releasing. Obtained supplement imitates dietary vine properties.

EFFECT: product of increased antioxidant properties.

22 cl, 1 tbl, 13 ex

Description

The present invention relates to antioxidant complexes derived from vinasse distillery, from which solid, semi-solid or liquid preparations for oral administration as food additives are prepared. These preparations include the same antioxidant complexes, including polyphenolic compounds contained in wine, for example, resveratrols and bioflavonoids, for example, anthocyanins and polyphenols, but do not contain ethyl alcohol. Thus, these preparations do not affect the liver and central nervous system, as in the use of wine, while providing well-known advantages inherent in the natural components of wine.

Fruits, vegetables, and beverages derived from them contain important components of non-nutritive nutrition that exhibit antioxidant activity. The wine identified more than 300 organic compounds belonging to the classes of carboxylic acids, mono- and disaccharides, amines, polyphenolic compounds, volatile compounds and pigments. The main source of antioxidant activity are polyphenolic compounds, which also affect the taste and color of wine. In particular, important antioxidants are flavonoids, including catechins (catechin, epicatechin), flavone glycosides, flavonols (myricetin, quartzetin, rutin, camferol, isoramnetin), flavanones, anthocyanins (dolphinin, cyanine, petunin, peonidine, malvinin) stilbenes (cis and trans resveratrols and their glycosides), present in high concentrations in the skin and seeds of red grapes and in red wine.

Wine also contains carboxylic acids, for example, citric and tartaric acids; benzoic acids, for example, gallic acid, protocatechuic acid, vanillic and hydroxybenzoic acid; cinnamic acids, for example, caffeic, coumaric, ferulic acids and others (M. Calull et al., J. Chromatogr., 590, 212-22, 1992; F. Mattivi, G. Nicolini, Biofactors, 6, 445-448, 1997; T.N. Frenkel et al., J. Agric. Food Chem., 43, 890-894, 1995).

Phenolic groups provide many benefits due to their antioxidant, free radical inhibitory, and metal-capturing activity (Catherine A. Rice-Evans et Lester Packer, Flavonoids in Health and Disease, Marcel Dekker, NY, 1998). These groups protect a person from cardiovascular diseases and thrombosis caused by an excess of free oxygen radicals. Resveratrols, in particular, can inhibit platelet aggregation (RJGryglewski et al., Biochem. Pharmacol., 36, 317-322, 1987) and prevent the oxidation of low density lipoproteins (LDL) (E.N. Frankel et al., Lancet, 341, 454-457, 1993). In addition, due to the presence of the above compounds, moderate consumption of wine can increase the antioxidant ability of human serum (Whitehead et al., Clin. Chem., 41, 32-35, 1995), can increase plasma α-tocopherol and retinol (P Simonetti et al., Alcohol Clin. Exp. Res., 19 (2), 517-522, 1995) and lower fibrinogen levels (N. Pellegrini et al., Eur. J. Clin. Nutr., 50, 209- 213, 1996).

Finally, it was found that a glass of red wine provides the body with significantly more flavonoids than vegetables (P. G. Pietta et al., Dietary flavonoids and oxidative stress in "Natural antioxidants and food quality in atherosclerosis and cancer prevention", JTKumpfalien, Cambridge , 249-255, 1996), but alcohol causes significant adverse side effects (M. Gronbaek et al., Biochem. Pharmacol., 36, 317-322, 1987), especially in the case of heavy consumption of wine.

It is also clear that alcohol contributes to the beneficial effect of wine consumption, since it provides the solubility of antioxidant complexes, in particular phenols, in the intestine (Goldberg, Clin. Chem. 41, 14-16, 1995), so bioavailability antioxidant complexes, in particular polyphenols present in grapes (or in its juice, skin and seeds), are lower than the bioavailability of the same polyphenols contained in wine.

Thus, an object of the present invention is to provide a food grade substance capable of completely replacing the daily glass of wine recommended in the medical literature whenever wine consumption is undesirable for dietary or religious reasons.

Another objective of the present invention is to provide a non-alcoholic, in particular ethanol-free, dietary supplement capable of providing the body with antioxidant complexes usually found in wine, which are very beneficial for the body.

Another objective of the present invention is the creation of a food supplement, providing such an absorption of antioxidant complexes, usually contained in wine, which is constant in time.

Another objective of the present invention is to provide a method for the production of food additives, and this method uses cheap and easily available raw materials and does not change the antioxidant complexes contained in it.

The above and other tasks, which will be clear from the following description, are solved by means of a food additive obtained from wine stillage. In particular, according to one aspect of the present invention, there is provided a dietary supplement of wine stillage suitable for oral administration. According to another aspect of the present invention, there is provided a method for producing a food additive in the form of a solid or liquid preparation from a wine bard.

Barda is the water residue obtained from the separation of wine intended for the production of edible alcohol in the distillery industry. Barda is a material to be disposed of. It also contains all the classes of compounds indicated above (carboxylic acids, mono- and disaccharides, amines, polyphenolic compounds and pigments), only without ethyl alcohol and partially aromatic volatile compounds.

As an example, one liter of red wine can on average contain from 0.6 to 11 mg of resveratrol (depending on the area of origin) and gives about 0.7 L of distillery stillage with a residue of 0.5 to 2.5 wt.%, Containing most antioxidant complexes present in wine. All of the above compounds are potentially of great biological interest; however, being isolated from the alcohol fraction, they have such a low bioavailability that they are of little use to the body. For this reason, wine barda or its concentrates cannot be used as food additives that can mimic the dietary properties of wine.

The objective of the present invention is to avoid significant losses due to the inapplicability of bards through the use of the antioxidants contained in it and to eliminate the problem of its disposal. Therefore, according to the present invention, specific substances are added to the bard that can increase the solubility and absorption of its components in vivo (these substances are called “bioavailability promoters”) to restore all the dietary properties of wine. Indeed, the authors unexpectedly found that there are a number of compounds that are chemically heterogeneous, with a specific ability to restore ("promote") the bioavailability of the beneficial compounds contained in the bard, and therefore allowing the bard to be used as antioxidant food additives. According to the invention, the absorption of antioxidant complexes present in the wine bard can be restored using bioavailability promoters selected from the group consisting of polysaccharides (such as, for example, dextrans, maltodextrins and inulin) and amino acids, such as, for example, glycine, proline, leucine and lysine.

According to a preferred embodiment of the present invention, the absorption (and therefore the blood content) of the antioxidant complexes present in the vinasse becomes more constant over time with sustained release formulations. A constant absorption profile is difficult to obtain when consuming wine, since in this case the wine will have to be drunk in small portions continuously for 24 hours. Therefore, the present invention not only allows you to simulate the dietary properties of wine in general, but also makes these properties available in time in a more constant way; therefore, the body will be better protected from the constant effects of free radicals.

The authors also developed methods for preparing solid compositions that do not alter the active ingredients. Liquid forms are obtained directly from wine barda, preferably after the addition of bioavailability promoters, followed by filtration.

The starting products used in the present invention are preferably red squeezes and a moderately sweet bard from red wine, in which the concentration of resveratrols and anthocyanins is higher than in squeezes and bards from white or pink wine.

In the case of drinking preparations, polysaccharides, for example, dextrans, maltodextrins or inulin, or also amino acids, for example, glycine, proline, leucine and lysine, are added to the barda as bioavailability promoters to increase the in vivo uptake of nutritionally valuable compounds, namely antioxidant complexes . Of the dextrans, dextran 5 (molecular weight 5000) is preferably used, and of maltodextrins, maltodextrin having 9-12 dextrose equivalents (DE), in particular Maltrin® M500, is preferred. Vitamin C or extract of green tea, blueberries, strawberries or red currants, which increase antioxidant capacity, may be added to barda, especially from white and rosé wines. If necessary, for a more pleasant taste, substances that are preferably, but not necessarily present in wine, are added to the bard, for example, organic acids, sugars and amines, coloring and aromatic agents, such as, for example, limonene, diethyl succinate, hexyl acetate, trans-hexenol and citronellol. Then the solutions are filtered through a filter with a pore size of 0.45 μm and poured into vials or small bottles for drinks.

In the case of solid preparations for sachets, capsules and tablets, said solutions containing bioavailability promoters are preferably dried by freeze drying or spray drying. To improve granulation and pressing processes, the solid residue is then mixed with raw materials commonly used in the food industry as diluents, binders, sintering inhibitors and adsorbents. In another embodiment, drying the stillage can also be carried out prior to the addition of bioavailability promoters and / or optional additives.

Regarding the initial liquid bard, the bioavailability promoters used in the present invention are dextrans, inulin or maltodextrins at concentrations from 0.4 to 30% (g / 100 ml), and glycine, proline, leucine or lysine at concentrations from 0.12 to 2 % (g / 100 ml). The optional antioxidants used, especially for bards from white and rosé wines, are dry blueberry extract with 25% anthocyanidins, at a concentration of 0.015 to 0.1% (g / 100 ml), caffeine-free dry extract of green tea with 50% polyphenols, in concentrations from 0.1 to 2% (g / 100 ml), dry currant extract with 3.8% flavonoids, at a concentration of 0.013 to 0.08% (g / 100 ml) and vitamin C at a concentration of 0.2 to 2% (g / 100 ml).

In order to obtain solid forms, fillers, diluents, binders, such as, for example, lactose (qs) (preferably from 0.4 to 0.7% (g / 100 ml) in the case of a solution or from 12 to 30% in case of solids); starch, for example, from potato (qs) (preferably from 0.4 to 0.7% (g / 100 ml) in the case of a solution or from 6 to 25% in the case of a dry residue); microcrystalline cellulose (qs) (preferably from 0.7 to 1% (g / 100 ml) in the case of a solution or from 1 to 38% in the case of solids); mannitol (qs) and / or silicon dioxide (qs). In particular, lactose and cellulose allow direct compression of the powder or preparation of the granular product in a wet or dry manner. In a preferred embodiment of the invention, 10 to 50% hydroxypropyl methyl cellulose having a viscosity of 4000 rpm is also used to coat the sustained release tablets.

For drinking solutions, it is also possible to use preservatives, such as benzyl alcohol (0.5-1%) or sodium benzoate (0.02-0.5%), and, in addition, the addition of a stabilizer, for example, citric or tartaric acid, is already available in wine.

Analytical control

The following compounds were identified in the bard as such, as well as in antioxidant complexes obtained by concentrating it to the dry residue: resveratrol, quercetin and catechin, the total content of phenols and anthocyanins.

The total phenol content was determined by a method developed in the laboratory of the applicants, based on spectrometry in the UV-visible region. The red wine distillery and the complexes obtained from it were diluted 200 times with methanol, while the white wine distillery was diluted 40 times. As a comparison, a solution of catechin-methanol with a concentration of 10 mg / ml was used. Each determination was repeated 5 times. The analysis showed an absorption spectrum from 200 to 500 nm for all samples with a value of D.O. 280 nm. The total polyphenol content was calculated as the concentration of catechin (mg / ml).

Instead, it was determined using liquid chromatography with a UV / VIS detector and a 100 CN 250 × 4 mm column (Lichrosphere). The mobile phase was water: acetonitrile: methanol (90: 5: 5) at a flow rate of 1 ml per minute. The wavelength was established at 306 nm (D. M. Goldberg et al., J. Chromatogr., A 708, 89-98, 1995). The samples to be tested were dissolved in alcohol and diluted with a solution of 0.2 M phosphoric acid: acetonitrile (4: 1).

To determine the total content of anthocyanins, we used a method capable of determining the concentration of anthocyanins by changing the absorption of the test sample as a result of discoloration caused by interaction with sulfur dioxide. To this end, the sample was first diluted with ethanol and HCl; then water was added to its part and a solution of sodium bisulfite was added to the part. The difference in absorption of these two solutions made it possible to calculate the content of anthocyanins, mg / L.

Quercetin and catechin were determined simultaneously by the method developed by the authors using liquid chromatography with a UV / VIS detector (with a variable wavelength in the UV range) and a 125 × 4 mm column (Lichrosorb Diolo). The mobile phase was hexane: ethanol (70:30), acidified with phosphoric acid, at a flow rate of 0.8 ml per minute. The wavelength was set at 280 nm. The substances were diluted with ethyl alcohol, obtaining solutions with a concentration of 10 μg / ml, and 20 μl of this solution was introduced.

The peaks were distinct, and the retention time was approximately 6 minutes for quercetin and approximately 13 minutes for catechin.

Antioxidant ability

The antioxidant ability of bards and complexes was determined by the Miller-Rice-Evans method (N.J. Miller, C. Rice-Evance, Redox Rep., 2 (3), 161-171, 1996).

Chromogenic substance ABTS [2,2'-azinobis (3-ethylbenzothiazolin-6-sulfonate) in the presence of potassium persulfate was converted to the blue-green monocationic radical form ABTS ^{· +} . The addition of an antioxidant similar to vitamin E, called Trolox, causes - in proportion to it concentration - discoloration of the solution, the absorption of which was determined spectrographically at 734 nm Antioxidant ability (TAS) of the stillage and new products was determined by comparing the absorption of the solution of the radical in contact with Trolox, with the absorption of the studied image and, expressed in its "eq mM Trolox / kg.".

Table 1 shows, by way of example, the concentrations of some polyphenolic compounds in red wine bard (Recioto, 1998 harvest), in the freeze-dried Recioto bard, in spray-dried pink wine bard of the 1998 harvest, in Pinot grigio bard of the Veneto region of the crop 1999 and their antioxidant ability.

Table 1 Sample Resveratrol, mcg / ml Catechin, mcg / ml Quercetin, mcg / ml Total phenol content, mcg / ml Anthocyanins, mcg / ml TAS mM Trolox Barda Recioto 3,7 1.9 0.02 24 88.9 3.9 Bard freeze-drying Example 3 3,5 1.9 0.02 26 246 6.3 Barda spray drying Example 5 1.8 1.7 0,03 21 153 4.0 Barda Pinot grigio 0.05 0.02 Not def. 16,2 Not def. 0.6

experimental part

The following examples illustrate the claimed invention. These examples are illustrative and in no way intended to limit the scope of the invention as defined in the appended claims.

Example 1

Red wine bard drinking solution with dextran

Dextran 5 (20 g, M.M. 5000), fructose (0.6 g), dry blueberry extract (0.15 g), benzoate were added to red wine bard (1 l), which had a wine and moderately sweet taste. sodium (50 mg) and citric acid (0.2 g). The resulting solution was filtered through a 0.45 μm filter and bottled. Received a drink with a pleasant taste, with antioxidant ability equal to 4.12 mm Trolox.

Example 2

Barda from white wine containing maltodextrin and freeze dried

Maltodextrin (100 g), namely Maltrin® M500, blueberry extract (1 g) and green tea extract (1 g) is added to white wine bard (1 l). The resulting solution was filtered through a 0.45 μm filter and freeze dried in accordance with a cycle that included the following temperatures: -35 ° C during preliminary freezing, -10 ° C during freeze drying, 0 ° C, + 10 ° C and 28 ° C during drying. A vacuum of 7.4 · 10 ^-2 mbar was maintained. The resulting light pink granular powder (117 g) had an antioxidant capacity of 4.2 mM Trolox.

Example 3

Red wine barda containing maltodextrin and freeze dried

Maltodextrin (110 g), namely Maltrin® M500 and blueberry extract (0.7 g), was added to red wine bard (1 L). The resulting solution was filtered and freeze dried as described in Example 2. The obtained residue (124.5 g) in the form of a hygroscopic powder of squeezed color had an antioxidant capacity of 6.3 mM Trolox.

Example 4

Red wine barda containing inulin and glycine and freeze dried

Inulin (5 g), glycine (1.8 g), green tea extract (2 g) and lactose (5 g) are added to red wine bard (1 l). The resulting solution was filtered and freeze dried in accordance with the cycle described in example 2. The resulting dry residue (27.4 g) in the form of a pink-purple compact powder had an antioxidant capacity of 8.9 mm Trolox.

Example 5

Rose wine barda containing dextran and spray dried

Dextran 5 (5 g, M.M. 5000), blueberry extract (1 g), lactose (6 g) and starch (5 g) were dissolved in rose wine bard (1 l). The resulting solution was filtered through a 0.45 μm filter and spray dried using mini-spray drying (Mini Buchi); jet pressure 800 mbar, temperature: inlet 130 ° С, outlet 50 ° С, 100% suction.

The resulting light pink granular powder (32 g) had an antioxidant capacity of 4.0 mM Trolox.

Example 6

Red wine barda containing dextran and spray dried

Dextran 5 (4 g, M.M. 5000), microcrystalline cellulose (8 g) and vitamin C (3 g) were dissolved in bard from dark red wine (1 l). The resulting solution was filtered and dried as described in Example 5. The resulting garnet red fine powder (292 g) had an antioxidant capacity of 4.5 mM Trolox.

Example 7

Getting granular product

The product described in example 3 was mixed with microcrystalline cellulose (2 g) and wetted with 5% PVP-ethanol solution (20 ml) to obtain a granulation mixture. The wet mass was sieved through a No. 25 sieve, dried in an oven with air circulation at 35 ° C and sorted by size through the same sieve.

Example 8

Getting capsules

Silica precipitate (0.4 g) was added to the granular product described in Example 1. The resulting product managed to fill one hundred and twenty 1 g capsules.

Example 9

Bag making

To the granular product described in Example 7, citric acid (3 g), sodium bicarbonate (3 g), fructose (2 g), flavor (1 g) and silica (silicon dioxide) (0.4 g) were added to obtain the product , which was divided into six 2 g sachets.

Example 10

Pill making

The product described in example 4 was wetted with 4% PVP solution (10 ml). The wet mass was sieved through a No. 25 sieve, dried in an oven with air circulation at 35 ° C and sorted by size through the same sieve. Microcrystalline cellulose (1 g), fructose (1.5 g), flavor (0.25 g), magnesium stearate (0.35 g) and talc (0.35 g) were added with simple stirring. This powder was pressed on a hand press (applied pressure: 1000 kg) using hollow dies with a diameter of 10 mm, and received 55 tablets of 0.5 g.

Example 11

Chewable Tablets

To the product described in Example 4, microcrystalline cellulose (1 g), fructose (2 g), flavor (0.4 g), magnesium stearate (0.3 g) and talc (0.3 g) were added with simple stirring.

This powder was pressed on a press using flat dies with a diameter of 13 mm with a crusher, and 25 tablets of 1 g were obtained.

Example 12

Making Effervescent Tablets

The remainder of Example 6 was mixed with lactose (4.15 g), starch (2 g), fructose (2 g), flavor (0.5 g), powdered enocyanin (grape skin extract) (10 mg), citric acid (2 5 g) and sodium bicarbonate (2.5 g). This powder was pressed on a press using flat dies with a diameter of 20 mm. Tablets weighing 2 g were immediately enclosed in blister packs.

Example 13

Sustained Release Tablets

The product described in example 4 was wetted with 4% PVP solution (10 ml). The wet mass was sieved through a No. 25 sieve, dried in an oven with air circulation at 35 ° C and sorted by size through the same sieve. Microcrystalline cellulose (1 g), magnesium stearate (0.35 g) and talc (0.35 g) were added with simple stirring.

The granular product was pressed on a hand press designed to produce one tablet using a 10 mm diameter hollow die, and 0.5 g tablets were obtained.

Hydroxypropyl methylcellulose (6 g), magnesium stearate (250 mg) and colloidal silica (150 mg) were mixed in a turbulator for 15 minutes. The previously used stamp was replaced by a hollow stamp with a diameter of 12 mm; then the individual cores were coated with a mixed powder. Specifically, the matrix was filled with powder (53 mg), core, again with powder (53 mg), and finally pressed.

By the double-pressing technique, 60 sustained release tablets were obtained, each weighing 0.6 g (± 5%).

Industrial applicability

The present invention provides compositions derived from vinasse distillery with the addition of bioavailability promoters that can be used as food additives capable of mimicking the dietary properties of wine, but without the toxic effects of alcohol. In addition, delayed-release wine bard compositions make the beneficial effects of wine constant over time; in addition, their effect is similar to the effect of regular consumption of wine.

To the described liquid and solid food additives, if it is required, in particular, when using bards from white and rosé wines, which, as the above analytical data show, contain quite a bit of resveratrol, additional antioxidants can be added.

Solid derivative bards are obtained by freeze drying and spray drying. These processes are fast, inexpensive, and do not degrade antioxidant complexes.

Tablets, capsules or granular products (preferably in the form of sustained release preparations) provide an alternative to drinking solutions and are especially preferred for those who constantly use these compositions against the imbalance of radicals caused by environmental pollution, tobacco smoking, stress, prolonged muscle effort, malnutrition , alcoholic beverages, certain medications, pathogens, inflammatory and neoplastic diseases.

Claims (22)

1. A nutritional supplement suitable for oral administration containing an antioxidant complex derived from vinasse, in combination with one or more bioavailability promoters selected from the group consisting of polysaccharides and amino acids. 2. The nutritional supplement of claim 1 in the form of a sustained release composition. 3. The nutritional supplement according to claim 1, wherein the antioxidant complexes are substances derived from vinasse from red wine. 4. The nutritional supplement according to claim 1, wherein the antioxidant complexes are substances derived from vinasse from white or rosé wines. 5. The nutritional supplement according to claim 1, additionally containing antioxidant additives selected from the group consisting of vitamin C, extracts of blueberries, currants, strawberries and / or green tea. 6. The nutritional supplement according to claim 1, further comprising food excipients selected from the group consisting of flavorings, preservatives, colorants and / or sweeteners. 7. The nutritional supplement according to claim 6, wherein the flavorings are selected from the group consisting of limonene, diethyl succinate, hexyl acetate, trans-hexenol and / or citronellol. 8. The nutritional supplement according to claim 1, in which the antioxidant complexes contain one or more polyphenolic compounds, including one or more flavonoids selected from the group consisting of catechins, flavonglycosides, flavonols, flavanones, anthocyanins, anthocyanidins and stilbenes. 9. The food supplement of claim 8, wherein the catechins are selected from catechin and / or epicatechin. 10. The nutritional supplement of claim 8, wherein the flavonols are selected from the group consisting of myricetin, quercetin, rutin, camferol, isoramnetin. 11. The nutritional supplement of claim 8, wherein the anthocyanins are selected from the group consisting of dolphinin, cyanine, petunin, peonin, malvin. 12. The nutritional supplement of claim 8, wherein the stilbenes are selected from cis and trans resveratrols and their glycosides. 13. The food supplement of claim 1, wherein the polysaccharides are selected from the group consisting of dextrans, maltodextrins, and inulin. 14. The nutritional supplement of claim 1, wherein the amino acids are selected from the group consisting of glycine, proline, leucine and lysine. 15. The food supplement according to claim 1 in solid, semi-solid and liquid form. 16. The nutritional supplement according to claim 1 in the form of capsules, pills, tablets, granules, syrup or drinking bottles. 17. The food supplement of claim 16 in the form of sustained release tablets. 18. The use of a combination of antioxidant complexes derived from vinasse vinasse with bioavailability promoters selected from the group consisting of polysaccharides and amino acids for the manufacture of a sustained release food supplement capable of producing an effect similar to the effect of regular consumption of wine. 19. The use according to claim 18, wherein fillers are added suitable for the manufacture of a sustained release food supplement, the effect of which is similar to the effect of regular consumption of wine. 20. A method of manufacturing a food supplement capable of simulating the dietary properties of wine, comprising mixing the following ingredients: (a) wine bard, and (b) one or more bioavailability promoters selected from the group consisting of polysaccharides and amino acids, preferably according to claims 13 and 14. 21. The method according to claim 20, in which (c) additives are additionally added to the mixture, such as the excipients indicated in claim 19 and / or the food excipients indicated in claim 6. 22. The method according to claim 20 or 21, in which the wine vinasse is dried by freezing or spraying before or after mixing with components (b) and (c).