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    • 专利摘要:
    Stevia glycosyl composition The present invention relates to stevia glycosyl compositions prepared from stevia rebaudiana bertoni steviol glycosides. Glycosylation was performed by cyclodextrin glucanotransferase using starch as the source of glucose residues. the short chain stevia glycosyl compositions were purified to> 95% total steviol glycoside content. The compositions may be used as sweetness enhancers, flavor enhancers and sweeteners in foods, beverages, cosmetic and pharmaceutical substances.
    公开号:BR112013020891B1
    申请号:R112013020891-0
    申请日:2011-05-04
    公开日:2019-11-12
    发明作者:Markosyan Avetik
    申请人:Purecircle Usa Inc；
    IPC主号:
    专利说明:

    "PROCESS FOR THE PRODUCTION OF A GLYCOSIL STEVIA COMPOSITION HIGHLY PURIFIED"
    Cross-reference to related orders [001] This patent application is partly a continuation application and claims priority benefit to US Patent Application Serial No. 13 / 029,263, filed on February 17, 2011 and the patent application North American Serial No. 13 / 074,179, filed on March 29, 2011.
    Background of the invention
    Field of the invention [002] The invention relates to a process for producing a highly purified food ingredient from the extract of the Stevia rebaudiana Bertoni plant and its use in various food products and beverages.
    Description of the related technique [003] Today, sugar alternatives are receiving increasing attention due to the awareness of many diseases, in conjunction with the consumption of sugar-rich foods and drinks. However, many artificial sweeteners, such as dulcin, sodium cyclamate and saccharin have been banned or restricted in some countries due to concerns about their safety. Therefore, natural non-caloric sweeteners are becoming increasingly popular. Stevia rebaudiana Bertoni fennel produces a series of diterpene glycosides, which have a high intensity of sweetness and sensory properties superior to those of many other high potency sweeteners.
    [004] The sweet glycosides mentioned above have a common aglycone, steviol, and differ in the number and type of carbohydrate residues at positions C13 and C19. Stevia leaves are capable of accumulating up to 10-20% (on a dry weight basis) of steviol glycosides. The main glycosides found in Stevia leaves are Rebaudioside A (2-10%), Stevioside (2-10%) and Rebaudioside C (1
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    2%). Other glycosides such as Rebaudioside B, D, E and F, Steviolbioside and Rubusoside are found at much lower levels (about 0-0.2%).
    [005] Two main glycosides - Stevioside and Rebaudioside A - have been extensively studied and characterized in terms of their suitability as high intensity commercial sweeteners. Stability studies in carbonated beverages confirmed their heat and pH stability (Chang S.S., Cook, J.M. (1983) Stability studies of stevioside and Rebaudioside A in carbonated beverages.J. Agric. Food Chem. 31: 409-412).
    [006] Steviol glycosides differ from each other not only in molecular structure, but also in their taste properties. Typically, stevioside is found to be 110 - 270 times sweeter than sucrose, Rebaudioside A between 150 and 320 times, and Rebaudioside C between 40-60 times sweeter than sucrose. Dulcoside A is 30 times sweeter than sucrose. Rebaudioside A has a less astringent, less bitter, and less persistent aftertaste, thus having the most favorable sensory attributes in the main steviol glycosides (Tanaka O. (1987) Improvement of taste of natural sweetners. Pure Appl. Chem. 69: 675 -683; Phillips KC (1989) Stevia: steps in developing a new sweetener. In: Grenby TH ed. Developments in sweeteners, vol. 3. Elsevier Applied Science, London 1-43).
    [007] The methods for extracting and purifying sweet glycosides from the Stevia rebaudiana plant using water or organic solvents are described, for example, in US Patent Numbers 4,361,697, 4,082,858, 4,892,938, 5,972,120, 5,962,678, 7,838,044 and 7,862,845.
    [008] However, even in a highly purified state, steviol glycosides still have undesirable taste attributes, such as bitterness, residual sweet taste, licorice flavor, etc. One of the main obstacles to success in the commercialization of stevia sweeteners are these attributes of unwanted taste
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    3/21 vehicles. These flavor notes have been shown to become more prominent as the concentration of steviol glycosides increases (Prakash I., DuBois GE, Clos JF, Wilkens KL, Fosdick LE (2008) Development of rebiana, a natural, non -caloric sweetener. Food Chem. Toxicol., 46, S75-S82).
    [009] Some of these undesirable properties can be reduced or eliminated by submitting steviol glycosides to the intermolecular transglycosylation reaction, when new carbohydrate residues are attached to the initial molecule at positions C13 and C19. Depending on the number of carbohydrate residues in these positions, the quality and potency of the taste of the compounds will vary.
    [010] Pululanase, isomaltase (Lobov SV, Jasai R., Ohtani K., Tanaka O. Yamasaki K. (1991), Enzymatic production of sweet stevioside derivatives: transglycosylation by glucosidases. Agric. Biol. Chem. 55: 2959-2965 ), β-galactosidase (Kitahata S., Ishikawa S., Miyata T., Tanaka O. (1989) Production of rubusoside derivatives by transglycosylation of various β-galactosidase. Agric. Biol. Chem. 53: 2923-2928), and dextran sucrase (Yamamoto K., Yoshikawa K., Okada S. (1994), Effective production of glucosyl-stevioside by a-1,6-transglucosylation of dextran dextranase.Biosci. Biotech. Biochem. 58: 1657-1661) as transglycosylation enzymes, together with pullulan, maltose, lactose and partially hydrolyzed starch, respectively, as donors of glycosidic residues.
    [011] The transglycosylation of steviol glycosides was also performed by the action of cyclodextrin glucanotransferases (CGTase) produced by Bacillus stearothermophilus (US patent numbers 4,219,571 and 7,807,206) as a result, α-1,4-glycosyl derivatives were formed with degree of polymerization up to 10.
    [012] It has been shown that (Tanaka O. (1987) Improvement of taste of natural sweetners. Pure Appl. Chem. 69: 675-683) that the taste and sweetness power profile of glucose derivatives are largely dependent the number of additional a-1,4-glycosyl derivatives, that is, the degree of polymerization of the a-1,4-glycosyl chain.
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    However, in most transglycosylated stevia products, the degree of polymerization is generally below nine. As with any reaction, the transglycosylation reaction is inhibited by its products, and the increase in α-1,4glycosyl residues is inhibited by the reaction products, in particular short-chain malto-oligosaccharides.
    [013] Therefore, it is necessary to develop a simple process of preparing high purity glycosyl stevia products with a longer chain length α1,4-glycosyl and a better flavor profile.
    Summary of the invention [014] The present invention is intended to overcome the disadvantages of existing Stevia sweeteners. The invention describes a process for producing a high purity food ingredient from the extract of the Stevia rebaudiana Bertoni plant and its use in various food products and beverages, as a sweetness and flavor modifier.
    [015] The invention, in part, concerns an ingredient comprising glycosylated derivatives of steviol glycosides from the Stevia rebaudiana Bertoni plant. Steviol glycosides are selected from the group consisting of stevioside, Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside rubusoside, as well as other steviol glycosides found in the Stevia rebaudiana plant Bertoni and his mixtures.
    [016] The invention, in part, relates to a process for the production of an ingredient containing stevioside glycosylated forms, Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside , rubusoside, as well as other steviol glycosides found in the Stevia rebaudiana Bertoni plant. The process can be an enzymatic transglycosylation process using CGTases produced by cultu
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    5/21 ras of Bacillus stearothermophilus. The process can include the steps of discoloration, desalination and removal of malto-oligosaccharides. Discoloration can be performed using activated carbon. Desalination can be carried out by passing through ion exchange resins and / or membrane filters. The removal of malto-oligosaccharides can be carried out by passing through a macroporous polymeric resin.
    [017] In the invention, Stevia extract sold by PureCircle (JiangXi) Co., Ltd. (China), containing stevioside (28-30%), Rebaudioside A (50-55%), Rebaudioside C (9-12%) , Rebaudioside F (1-3%) and other glycosides adding the total content of steviol glycoside of at least 95%, was used as starting material. Alternatively stevia extracts with different proportions of steviol glycosides, as well as highly purified steviol glycosides such as Rebaudioside A, stevioside, Rebaudioside D, rubusoside, etc. can be used as starting materials.
    [018] The starting material was subjected to enzymatic transglycosylation by the action of cyclodextrin glycosyltransferase (CGTase) in the presence of starch as a glucose donor. As a result, α-1,4-glycosyl derivatives were formed with a degree of polymerization up to 9. Then, the malto-oligosaccharides from the reaction mixture obtained were removed by Amberlite XAD7 HP resin. The resulting mixture of α-1,4-glycosyl derivatives (with a degree of polymerization up to 9) was subjected to the second enzymatic transglycosylation by CGTase in the presence of starch as a glucose donor. As a result of the second glycosylation, α-1,4-glycosyl derivatives were formed with a degree of polymerization up to 20. Maltooligosaccharides obtained during the second glycosylation were removed by Amberlite XAD7 HP resin. Then, the mixture obtained from a-1,4-glycosyl derivatives (with a degree of polymerization up to 20) was discolored, deionized, concentrated and spray dried.
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    6/21 [019] The products obtained were applied in various foods and beverages such as sweeteners, sweeteners and flavor modifiers, including ice cream, cookies, breads, fruit juices, dairy products, bakery products and confectionery.
    [020] It should be understood that both the previous general description and the following detailed description are exemplary and explanatory and are intended to provide a further explanation of the invention as claimed.
    Brief description of the drawings [021] The accompanying drawings are included to provide a better understanding of the invention. The drawings illustrate embodiments of the invention and together with the description serve to explain the principles of the embodiments of the invention.
    [022] FIG. 1 shows a high performance liquid chromatogram of transglycosylated Stevia extract containing α-1,4-glycosyl derivatives with up to nine α-1,4-glycosyl residues;
    [023] FIG. 2 shows a high performance liquid chromatogram of transglycosylated Stevia extract containing a-1,4-glycosyl derivatives with up to twenty α-1,4-glycosyl residues.
    Detailed description of the invention [024] The advantages of the present invention will become more evident from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become evident to those skilled in the art. technique from this detailed description.
    [025] Stevia extract commercialized by PureCircle (Jiangxi) Co., Ltd. (China), containing stevioside (28-30%), Rebaudioside A (50-55%), Rebaudioside C
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    7/21 (9-12%), Rebaudioside F (1-3%) and other glycosides (hereinafter, collectively steviol glycosides) adding a total steviol glycoside content of at least 95%, was used as a material of departure. Alternatively stevia extracts with different proportions of steviol glycosides, as well as highly purified steviol glycosides such as Rebaudioside A, stevioside, Rebaudioside D, rubusoside etc., can be used as starting materials.
    [026] The HPLC analysis of raw materials and products was performed using an Agilent Technologies 1200 Series liquid chromatograph (USA), equipped with the Zorbax-NH2 column (4.6X250mm). The mobile phase was an acetonitrile-water gradient from 80:20, v / v (0-2 min) to 50:50, v / v (2-70 min.) A diode array detector set at 210 nm was used as the detector.
    [027] Transglycosylation was performed by cyclomaltodextrin glucanotransferases (CGTases; EC 2.4.1.19) produced by Bacillus stearothermophilus St-100 (PureCircle Sdn Bhd Collection of Industrial Microorganisms - Malaysia). However, any other CGTase or enzyme having intermolecular transglycosylation activity can be applied as well. The enzyme may be in the form of a cell-free culture broth, concentrated liquid cell-free culture broth, spray-dried or lyophilized cell-free culture broth, or high-purity protein. Free and immobilized enzyme preparations can be used.
    [028] The activity of CGTase preparations was determined according to the procedure described in Hale W.S., Rawlins L.C. (1951) Amylase of Bacillus macerans.Cereal Chem. 28, 49-58.
    [029] Starches of different origin can be used as donors of glycosyl units, such as derivatives of wheat, corn, potatoes, tapioca and sago.
    [030] The starch was subjected to partial hydrolysis (liquefaction) before the transglycosylation reaction. The dextrose equivalent of the partially hydrolyzed starch can be in the range of about 10-25, preferably about 12-16. Any
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    8/21 enzyme capable of hydrolysis of starch can be used for liquefaction, such as αamylases, β-amylases, etc. In one embodiment, mixtures of CGTase and α-amylase are preferred as liquefaction enzymes.
    [031] α-amylase activity is expressed in Kilo Novo α-amylase Units (KNU). A KNU is the amount of α-amylase that, under standard conditions (pH 7.1; 37 ° C), dextrinizes 5.26 g of dry starch substance per hour.
    [032] The liquefaction mixture contains about 0.001-0.2 KNU, preferably about 0.05-0.1 KNU of α-amylase per one CGTase unit.
    [033] The use of α-amylase in liquefaction allows to achieve higher yields in activated carbon filtration. When CGTase is used as the only liquefaction enzyme, the filtration rate is about 10-15 L / hr per 1m 2 of the filter surface. If liquefaction enzymes are mixed (comprising α-amylase and CGTase), the filtration rate is twice as fast - about 2030 L / hr per 1 m 2 of the filter surface.
    [034] The ratio of starch and CGTase in the liquefaction mixture is about 0.1-0.5 units per gram of starch, preferably about 0.2-0.4 units per gram.
    [035] The concentration of starch in the liquefaction mixture is about 1540% (w / w), preferably about 20-30%.
    [036] Liquefaction is carried out at about 70 - 90 ° C for about 0.5 - 5 hours, preferably about 1 - 2 hours.
    [037] After liquefaction, the reaction mixture is subjected to thermal inactivation of α-amylase under low pH conditions. The preferred pH range for inactivation is about pH 2.5 to pH 3.0 and the preferred temperature is about 95 - 105 ° C. The duration of thermal inactivation is about 5 - 10 minutes.
    [038] After deactivation, the pH of the reaction mixture is adjusted to about pH 5.5 - 6.5 and steviol glycosides are added to the mixture and dissolved. THE
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    9/21 preferred ratio of steviol glycosides to starch (kg of steviol glycosides per 1 kg of starch) is about 0.5 - 1.5, preferably about 0.8 - 1.2.
    [039] A second part of the CGTase preparation is added and the first transglycosylation reaction is conducted at about 65 ° C for about 24 48 hours. The amount of the second part of CGTase is about 0.2 - 4 units of CGTase per gram of solids, preferably about 0.5 - 1.2 units per gram of solids.
    [040] After completion of transglycosylation, the reaction was stopped by heating to about 95 ° C for about 15 minutes to inactivate the enzyme. As a result, a mixture of α-1, 4-glycosyl derivatives with a degree of polymerization up to 9 was obtained. In order to remove the short-chain malto-oligosaccharides, which inhibit further a-1 chain elongation, 4-glycoside, the reaction mixture was passed through a column packed with Amberlite XAD7 HP macroporous adsorbent resin. The steviol glycosides and their glycosylated derivatives were adsorbed onto the resin and subsequently eluted by aqueous ethanol. The resulting aqueous ethanol eluate, containing the glycosylated steviol glycosides, was evaporated, concentrated and spray dried to obtain transglycosylated Stevia extract containing glycosyl derivatives with up to nine a-1,4 glycosyl residues.
    [041] A second part of starch was subjected to partial hydrolysis (liquefaction), as described above.
    [042] After liquefaction, the transglycosylated Stevia extract obtained during the first glycosylation (with up to nine a-1,4-glycosyl residues) was added. The preferred ratio of the transglycosylated Stevia extract to starch (kg of transglycosylated Stevia extract per 1 kg of starch) is about 0.5 - 1.5, preferably about 0.8 - 1.2.
    [043] Another part of the CGTase preparation was added and the second area
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    10/21 transglycosylation was carried out at about 65 ° C for about 24 - 48 hours. The amount of this part of CGTase is about 0.2 - 4 units of CGTase per gram of solids, preferably about 0.5 - 1.2 units per gram of solids.
    [044] After completion of transglycosylation, the reaction was stopped by heating to about 95 ° C for about 15 minutes to inactivate the enzyme. As a result, a mixture of a-1,4-glycosyl derivatives with a degree of polymerization up to 20 was obtained.
    [045] Malto-oligosaccharides were removed from the reaction mixture using Amberlite XAD7 HP resin as described above. The steviol glycosides and their glycosylated derivatives were adsorbed onto the resin and subsequently eluted by aqueous ethanol. The resulting aqueous ethanol eluate, containing glycosylated steviol glycosides, was treated with activated carbon to obtain a colorless reaction mixture. The amount of activated carbon was about 0.02 - 0.4 g per gram of solids, preferably about 0.05 - 0.2 g per gram of solids. The discolored solution was additionally desalted by passing through ion exchange resins, such as Amberlite FPC23 (type H + ) and Amberlite FPA51 (type OH - ). Other appropriate bleaching and desalting methods can be used, such as membrane filtration or other methods known in the art.
    [046] The desalted reaction mixture was further concentrated by means of a vacuum evaporator and dried by means of a spray dryer. Other appropriate methods of concentration and drying, such as membrane filtration, lyophilization, or other methods known in the art, can be used.
    [047] The resulting product was transglycosylated Stevia extract containing a-1,4-glycosyl derivatives with up to twenty a-1,4-glycosyl residues (Sample 2).
    [048] The transglycosylated Stevia extract can optionally be further purified by removing unreacted steviol glycosides. The ex
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    11/21 Dry transglycosylated Stevia tract powder is suspended in aqueous alcohol. The ratio of powder to aqueous alcohol (weight / volume) can vary from 1: 1 to 1:20, preferably from 1: 3 to 1:10. Aqueous alcohol contains 0 - 50% (vol), preferably 1 - 10% water. The suspension is stirred at 30 - 100 ° C, preferably 50 - 85 ° C for 1 - 24 hours, preferably 2 - 15 hours. Then, the suspended solids are separated by means of filtration. Any other technique known in the art, suitable for the separation of suspended solids from liquids, such as centrifugation, decanting, etc., can be used. The obtained solids are dried in a rotary drum vacuum dryer. Any other dryer known in the art can also be used. Alternatively, the separated solids can be dissolved in water, evaporated from traces of alcohol and spray dried.
    [049] The alcohols used in this optional step can be selected from the group consisting of alkanols, and are preferably selected from the group that includes methanol, ethanol, n-propanol, 2-propanol, 1-butanol and 2butanol.
    [050] The resulting product contains a low level of unmodified glycosides, even without the optional steviol glycoside removal step. As used herein, the terms low level of unmodified glycosides or low level of unreacted glycosides refer to glycoside levels of less than about 20%, and preferably less than about 15%, in an anhydrous base. In some embodiments, an unreacted glycoside level of less than about 12%, less than about 10% or even lower can be obtained using this method. Performing the optional steviol glycoside removal step results in even lower levels of unreacted steviol glycosides in the final product.
    [051] A small part of the purified transglycosylated Stevia extract containing a-1,4-glucosyl derivatives with up to nine a-1,4-glycosyl residues (obtained as
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    12/21 as described above) was separated and further subjected to a decolorization and desalination treatment (similar to Sample 2) to produce Sample 1.
    [052] The process used to prepare Sample 2 was repeated without removing the malto-oligosaccharides from the first transglycosylation mixture (containing a-1,4-glycosyl derivatives with up to nine a-1,4-glycosyl residues). This process resulted in Sample 3.
    [053] The analysis of the composition of each sample (Table 1) shows a similar composition for Samples 1 and 3, whereas Sample 2 had a higher concentration of high glycosyl derivatives (containing up to 20 a1,4-glycosyl residues ).
    TABLE 1
    Composition of glycosylated steviol glycoside samples
    Compounds Content,% Sample 1 Sample 2 Sample 3 Stevioside 3.1 1.6 2.9 Rebaudioside C 1.0 0.4 1.0 Rebaudioside A 6.1 2.8 5.8 Monoglycosyl-stevioside (StevG1) 7.4 3.7 7.5 Monoglycosyl-Rebaudioside A (RebAG1) 11.1 4.5 11.5 Diglycosyl-stevioside (StevG2) 8.4 4.8 8.8 Diglycosyl-Rebaudioside A (RebAG2) 9.6 5.3 9.7 Higher Glycosylated Derivatives up to G9 48.4 57.5 49.3 Higher glycosylated derivatives from G9 to G20 - 15.6 - Total content of unreacted glycosides 10.2 4.8 9.7 Total glycoside content 95.8 96.2 96.5
    [054] The sensory evaluation of the samples was carried out using aqueous solutions, with 20 panelists. Based on general acceptance, the most desirable and most undesirable samples were chosen. The results are shown in Table 2.
    TABLE 2
    Sensory evaluation of masters water system Judgment Sample 1 Sample 2 Sample 3 Most desirable 1 18 1
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    Powdered sweetness 120 80 120 comments Sweet, slightly bitter, astringent, soft lingering aftertaste, sweetness starts slowly sweet, light, soft, round, pleasant, similar to sucrose, without residual taste, the onset of sweetness is fast Sweet, slightly bitter, astringent, soft lingering aftertaste, sweetness starts slowly
    [055] As is evident from the results in Table 2, the quality of sweetness in Sample 2 was rated as superior.
    [056] The glycosyl stevia composition represented by Sample 2 shows comparable sweetness power (80 times sweeter compared to a 5% sucrose solution) with Control Samples 1 and 3 (120 times), however its flavor profile was clearly superior to that of the Control Samples.
    [057] The composition can be used as a sweetener, flavor enhancer and sweeteners in various food products and beverages. Non-limiting examples of food and beverage products include carbonated soft drinks, ready-to-drink drinks, energy drinks, isotonic drinks, low-calorie drinks, zero-calorie drinks, sports drinks, teas, fruit and vegetable juices, juice drinks, dairy drinks , yogurt drinks, alcoholic beverages, powdered drinks, bakery products, cookies, crackers, bakery mixtures, cereals, sweets, candies, caramels, chewing gums, dairy products, flavored milk, yogurts, flavored yogurts, fermented milk , soy sauce and other soy-based products, salad dressings, mayonnaise, vinegar, frozen desserts, meat products, fish meat products, canned and bottled foods, table sweeteners, fruits and vegetables.
    [058] In addition, the composition can be used in pharmaceuticals or pharmaceutical and cosmetic preparations, including, but not limited to toothpaste, mouthwash, syrup, chewable tablets, lozenges, vitamin preparations and the like.
    [059] The composition can be used as is, or in combination with other sweeteners, flavorings and other food ingredients.
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    14/21 [060] Non-limiting examples of sweeteners include steviol glycosides, stevioside, Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside, rubusoside, as well as other steviol glycosides found in the Stevia rebaudiana Bertoni plant and its mixtures, stevia extract, Luo Han Guo extract, mogroside, high fructose corn syrup, corn syrup, inverted sugar, fructo-oligosaccharides, inulin, inulo-oligosaccharides, coupling sugar , malto-oligosaccharides, maltodextins, corn syrup solids, glucose, maltose, sucrose, lactose, aspartame, saccharin, sucralose, sugar alcohols.
    [061] Non-limiting examples of flavors include flavors of lemon, orange, fruity, banana, grape, pear, pineapple, bitter almond, cola, cinnamon, sugar, cotton candy, vanilla.
    [062] Non-limiting examples of other food ingredients include flavors, acidulants, organic acids and amino acids, coloring agents, bulking agents, modified starches, gums, texturizers, preservatives, antioxidants, emulsifiers, stabilizers, thickeners, gelling agents.
    [063] The following examples illustrate various embodiments of the invention. It should be understood that the invention is not limited to the materials, proportions, conditions and procedures set out in the examples, which are illustrative only.
    Example 1
    Preparation of CGTase [064] A strain of Bacillus stearothermophilus St-100 was inoculated into 2,000 liters of sterile culture medium containing 1.0% starch; 0.25% corn extract; 0.5% (NH4) 2SO4 and 0.2% CaCOs (pH 7.0-7.5), at 56 ° C for 24 hours with continuous aeration (2,000 L / min) and agitation (150 rpm). The culture broth obtained was filtered using Kerasep 0.1 pm ceramic membrane (Novasep, France)
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    15/21 to separate the cells. The cell-free permeate was further concentrated twice in Persep 10kDa ultrafilters (Orelis, France). The enzyme activity was determined according to Hale, Rawlins (1951). A crude enzyme preparation was obtained with an activity of about 2 units / ml.
    Example 2
    Preparation of glycosyl stevia composition [065] 100 g of tapioca starch were suspended in 300 mL of water (pH
    6.5). 2 KU of α-amylase (Termamyl Classic, Novozymes, Denmark) and 30 units of CGTase obtained according to example 1 were added, and the liquefaction of the starch was carried out at 80 ° C for about one hour at an equivalent dextrose of about 15. The pH of the reaction mixture was adjusted to pH 2.8 with hydrochloric acid and the mixture was boiled at 100 ° C for 5 minutes to inactivate the enzymes. After cooling to 65 ° C, the pH was adjusted to pH 6.0 with sodium hydroxide solution. 100 g of stevia extract produced by PureCircle (Jiangxi) Co., Ltd. (China), containing 29.2% stevioside; Rebaudioside A 54.3%; Rebaudioside C 9.0%, Rebaudioside F (1.7%) and other glycosides equivalent to the total content of steviol glycosides of about 96.4% were added to the liquefied starch and stirred until a homogeneous solution was obtained. 200 units of CGTase were added to the solution and the mixture was maintained at a temperature of 65 ° C for 24 hours with continuous stirring. The reaction mixture obtained was heated to 95 ° C for 15 minutes to inactivate the enzymes. 20 g of activated carbon were added and the mixture was heated to 75 ° C and maintained for 30 minutes. The mixture was filtered and the filtrate was diluted with water at 5% solids content and passed through columns, each packed with 4000 ml of macroporous adsorbent resin Amberlite XAD 7HP. The columns were washed with 5 volumes of water and 2 volumes of 20% (v / v) ethanol. The adsorbed glycosides were eluted with 50% ethanol. The eluate obtained was passed through columns packed with ion exchange resins
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    Amberlite FPC23 (H + ) and Amberlite FPA51 (OH - ). The ethanol was evaporated and the decolorized and desalted aqueous solution was concentrated at 60 ° C under vacuum, then dried as a powder using a laboratory spray dryer. 151 g of the product were obtained (Sample 1).
    Example 3
    Preparation of composition of glucosyl stevia [066] 100 g of tapioca starch were suspended in 300 ml of water (pH
    6.5). 2 KNU of α-amylase (Termamyl Classic, Novozymes, Denmark) and 30 units of CGTase obtained according to Example 1 were added, and the liquefaction of the starch was carried out at 80 ° C for about one hour at an equivalent dextrose of about 15. The pH of the reaction mixture was adjusted to pH 2.8 with hydrochloric acid and the mixture was boiled at 100 ° C for 5 minutes to inactivate the enzymes. After cooling to 65 ° C, the pH was adjusted to pH 6.0 with sodium hydroxide solution. 100 g of transglycosylated stevia extract obtained according to Example 2 were added to the liquefied starch and stirred until a homogeneous solution was obtained. 200 units of CGTase were added to the solution and the mixture was maintained at a temperature of 65 ° C for 24 hours with continuous stirring. The obtained reaction mixture was heated to 95 ° C for 15 minutes to inactivate the enzyme. 20 g of activated carbon were added and the mixture was heated to 75 ° C and maintained for 30 min. The mixture was filtered and the filtrate was diluted with water at 5% solids content and passed through columns, each packed with 4000 ml of macroporous adsorbent resin Amberlite XAD 7HP. The columns were washed with 5 volumes of water and 2 volumes of 20% (v / v) ethanol. The adsorbed glycosides were eluted with 50% ethanol. The eluate obtained was passed through columns packed with ion exchange resins Amberlite FPC23 (H + ) and Amberlite FPA51 (OH - ). The ethanol was evaporated and the desalted and discolored aqueous solution was concentrated at 60 ° C under vacuum, then dried in a
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    17/21 powder in laboratory spray dryer. 140 grams of the product were obtained (Example 2).
    Example 4
    Preparation of stevia glycosyl composition [067] 100 g of tapioca starch were suspended in 300 ml of water (pH
    6.5). 2 KNU of α-amylase (Termamyl Classic, Novozymes, Denmark) and 30 units of CGTase obtained according to EXAMPLE 1 were added, and the starch was liquefied at 80 ° C for about one hour at an equivalent dextrose of about 15. The pH of the reaction mixture was adjusted to pH 2.8 with hydrochloric acid and the mixture was boiled at 100 ° C for 5 minutes to inactivate the enzymes. After cooling to 65 ° C, the pH was adjusted to pH 6.0 with sodium hydroxide solution. 100 g of stevia extract produced by PureCircle (Jiangxi) Co., Ltd. (China), containing 29.2% stevioside, 54.3% Rebaudioside A, 9.0% Rebaudioside C, Rebaudioside F (1, 7%) and other glycosides equivalent to the total content of steviol glycosides of about 96.4% were added to the liquefied starch and stirred until a homogeneous solution was obtained. 200 units of CGTase were added to the solution and the mixture was maintained at a temperature of 65 ° C for 24 hours with continuous stirring. The reaction mixture obtained was heated to 95 ° C for 15 minutes to inactivate the enzymes. 20 g of activated carbon were added and the mixture was heated to 75 ° C and maintained for 30 minutes. The mixture was filtered and the filtrate was passed through columns packed with ion exchange resins Amberlite FPC23 (H +) and Amberlite FPA51 (OH - ). 195 grams of the product were obtained.
    Example 5
    Preparation of glycosyl stevia composition [068] 100 g of tapioca starch were suspended in 300 mL of water (pH
    6.5). 2 KNU of α-amylase (Termamyl Classic, Novozymes, Denmark) and 30 units
    Petition 870180139077, of 10/8/2018, p. 26/37
    18/21 de CGTase obtained according to EXAMPLE 1 were added, and the starch liquefaction was carried out at 80 ° C for about an hour at an equivalent dextrose of about 15. The pH of the reaction mixture was adjusted to pH 2.8 with hydrochloric acid and the mixture was boiled at 100 ° C for 5 minutes to inactivate the enzymes. After cooling to 65 ° C, the pH was adjusted to pH 6.0 with sodium hydroxide solution. 100 g of transglycosylated stevia extract obtained according to Example 4 were added to the liquefied starch and stirred until a homogeneous solution was obtained. 200 units of CGTase were added to the solution and the mixture was maintained at a temperature of 65 ° C for 24 hours with continuous stirring. The obtained reaction mixture was heated to 95 ° C for 15 minutes to inactivate the enzyme. 20 g of activated carbon were added and the mixture was heated to 75 ° C and maintained for 30 min. The mixture was filtered and the filtrate was diluted with water at 5% solids content and passed through columns, each packed with 4000 ml of macroporous adsorbent resin Amberlite XAD 7HP. The columns were washed with 5 volumes of water and 2 volumes of 20% (v / v) ethanol. The adsorbed glycosides were eluted with 50% ethanol. The eluate obtained was passed through columns packed with ion exchange resins Amberlite FPC23 (H +) and Amberlite FPA51 (OH - ). The ethanol was evaporated and the desalted, decolorized aqueous solution was concentrated at 60 ° C under vacuum, then dried in powder form using a laboratory spray dryer. 105 g of the product were obtained (Sample 3).
    Example 6
    Low-calorie orange juice drink [069] Orange concentrate (35%), citric acid (0.35%), ascorbic acid (0.05%), red-orange coloring (0.01%), flavor of orange (0.20%), Rebaudioside A (0.003%) and different stevia glycosyl compositions (0.03% for Samples 1 and 3 and 0.04% for Sample 2) were mixed and completely
    Petition 870180139077, of 10/8/2018, p. 27/37
    19/21 dissolved in water (up to 100%) and pasteurized. Stevia glycosyl compositions were represented by Samples 1, 2 and 3, obtained according to Examples 2, 3 and 5, respectively.
    [070] The sensory evaluations of the samples are summarized in Table 3. The data shows that the best results can be obtained using the high purity glycosyl stevia composition (containing up to 20 α1,4-glycosyl residues) (Sample 2). Particularly the drinks prepared with Sample 2 exhibited a round and full flavor and mouthfeel profile.
    Table 3
    Evaluation of orange juice drink samples
    Sample comments Flavor Residual taste Mouthfeel N ° 1 Sweet notes of licorice Slight bitterness and aftertaste Not acceptable No. 2 High quality sweetness, pleasant taste similar to sucrose, round and balanced flavor Clean, without bitterness and without residual taste Complete No. 3 Sweet notes of licorice Slight bitterness and aftertaste Not acceptable
    [071] The same method can be used to prepare juices and juice drinks from other fruits, such as apples, lemons, apricots, cherries, pineapples, mangoes, etc.
    Example 7
    Low-calorie carbonated drink [072] A carbonated drink according to the formula shown below was prepared.
    Ingredients Amount, % Sample 1 Sample 2 Sample 3 Sucrose 5.5 5.5 5.5 Cola flavor 0.340 0.340 0.340 Orthophosphoric acid 0.100 0.100 0.100 Sodium citrate 0.310 0.310 0.310 Sodium benzoate 0.018 0.018 0.018 Citric acid 0.018 0.018 0.018
    Petition 870180139077, of 10/8/2018, p. 28/37
    20/21
    Rebaudioside A 0.003 0.003 0.003 Composition of glycosyl stevia 0.05 0.06 0.05 Carbonated water Up to 100 Up to 100 Up to 100
    [073] The sensory properties were evaluated by 20 panelists. The results are summarized in Table 4.
    Table 4
    Evaluation of low-calorie carbonated beverage samples
    Taste attributes Number of panel that detected the atibutoSample No. 1 Sample No. 2 Sample No. 3 Bitter taste 10 0 11 Astringent taste 12 0 10 Residual taste 14 0 14 comments Qualities of sweet taste Bitter aftertaste (10 of 20) Clean (20 of 20) Bitter aftertaste (12 of 20) General evaluation Satisfactory (3 of 20) Satisfactory (20 of20) Satisfactory (4 of 20)
    [074] The results above show that the drinks prepared using Sample 2 had better organoleptic characteristics.
    EXAMPLE 8
    Dietary cookies [075] Flour (50.0%), margarine (30.0%), fructose (10.0%), maltitol (8.0%), whole milk (1.0%), salt (0, 2%), baking powder (0.15%), vanillin (0.1%) and different stevia glycosyl compositions (0.03% for Samples 1 and 3, and 0.04% for Sample 2) were well kneaded in a pasta mixing machine. The obtained dough was molded and baked in the oven at 200 ° C for 15 minutes. Stevia glycosyl compositions were represented by samples 1, 2 and 3 obtained according to EXAMPLES 2, 3 and 5, respectively.
    [076] The sensory properties were evaluated by 20 panelists. The best results were obtained in samples prepared by high glycosyl stevia composition containing derivatives with up to 20 a-1,4-glycosyl residues (Sample 2). The panelists noticed a round and complete mouthfeel and flavor profile in cookies prepared with Sample 2.
    Petition 870180139077, of 10/8/2018, p. 29/37
    21/21
    Example 9
    Yogurt [077] Different compositions of glycosyl stevia (0.03% for Samples 1 and 3, and 0.04% for Sample 2) and sucrose (4%) were dissolved in low-fat milk. Stevia glycosyl compositions were represented by Samples 1,2 and 3, obtained according to EXAMPLES 2, 3 and 5, respectively. After pasteurization at 82 ° C for 20 minutes, the milk was cooled to 37 ° C. A starter culture (3%) was added and the mixture was incubated at 37 ° C for 6 hours and then at 5 ° C for 12 hours.
    [078] The sensory properties were evaluated by 20 panelists. The best results were obtained in samples prepared by high glycosyl stevia composition containing derivatives with up to 20 a, 1,4-glycosyl residues (Example 2). The panelists noticed a round and complete mouthfeel and flavor profile in samples prepared with Sample 2.
    [079] It should be understood that the previous descriptions and specific modalities presented here are merely illustrative of the best way of the invention and its principles, and that modifications and additions can be easily made by those skilled in the art without departing from the spirit and scope of invention, which is therefore understood to be limited only by the scope of the appended claims.
    权利要求:
    Claims (5)
    [1]
    1. Process for the production of a highly purified glycosyl stevia composition, CHARACTERIZED by the fact that it comprises the steps of:
    add starch in water to form a starch suspension;
    adding a mixture of α-amylase and CGTase to the starch suspension and incubating for about 0.5 to 2 hours at about 75 - 80 ° C, resulting in a first suspension of liquefied starch;
    inactivate α-amylase by heat treatment at low pH;
    cooling the first liquefied starch suspension and adjusting the pH to about 5.5 to 7.0;
    adding steviol glycosides to the first liquefied starch suspension, resulting in a first reaction mixture;
    add CGTase to the first reaction mixture and incubate for about 12 to 48 hours at about 55 - 75 ° C;
    removing non-reactive malto-oligosaccharides by contacting the first reaction mixture with the macroporous adsorbent resin and subsequently eluting diterpene glycosides adsorbed with aqueous ethanol to result in a first aqueous ethanol eluate containing glycoside;
    removing ethanol from the first aqueous ethanol eluate, resulting in a first aqueous eluate;
    concentrating and drying the first aqueous eluate to obtain the first dry stevia glycosyl composition;
    preparing a second suspension of liquefied starch in the same way as the first suspension of liquefied starch;
    adding the first dry glycosyl stevia composition to the second liquefied starch suspension, resulting in the second reaction mixture;
    add CGTase to the second reaction mixture and incubate for about 12 to 48 hours at about 55 - 75 ° C;
    inactivate the enzyme in the second reaction mixture by heat treatment;
    discolor the second reaction mixture;
    removing non-diterpene compounds by contacting the second discolored reaction mixture with macroporous adsorbent resin and subsequently eluting diterpene glycosides adsorbed with aqueous ethanol to obtain a second aqueous glycol containing eluate;
    desalting the second glycoside-containing aqueous ethanol eluate with ion exchange resins;
    remove ethanol from the second aqueous ethanol eluate, resulting in a second
    [2]
    2. Process, according to claim 1, CHARACTERIZED by the fact that the mixture of α-amylase and CGTase contains about 0.001 - 0.2 KNU of α-amylase per one unit of CGTase.
    2/4 aqueous eluate; and concentrating and drying the second aqueous eluate to obtain the highly purified stevia glycosyl composition;
    wherein the highly purified stevia glycosyl composition comprises steviol glycosides and their derivatives with up to twenty alpha-1,4-glycosyl residues.
    [3]
    3/4 decolorization is carried out using ion exchange resins or membranes, said membranes being selected from the group consisting of ultrafiltration, nanofiltration and reverse osmosis membranes.
    13. Process according to claim 1, CHARACTERIZED by the fact that the removal of malto-oligosaccharides and non-diterpene compounds is carried out with a plurality of sequentially linked columns packed with a macroporous adsorbent resin, followed by washing the columns with water, then washing with about 10 - 50% (v / v) of ethanol, disconnecting the columns and then eluting each column individually with 30 - 100% ethanol.
    14. Process, according to claim 1, CHARACTERIZED by the fact that desalination is carried out by passing the eluate through columns packed with ion exchange resins or membranes, said membranes being selected from the group consisting of ultrafiltration membranes, nanofiltration and reverse osmosis.
    15. Process according to claim 1, CHARACTERIZED by the fact that the highly purified stevia glycosyl composition has at least about 95% total steviol glycosides on an anhydrous basis.
    16. Process according to claim 1, CHARACTERIZED by the fact that the highly purified stevia glycosyl composition has less than 10% that unreacted steviol glycosides on an anhydrous basis.
    17. Sweetening composition, CHARACTERIZED by the fact that it comprises a highly purified glycosyl stevia composition produced by the process as defined in claim 1, and an additional sweetening agent selected from the group consisting of: stevia extract, steviol glycosides, stevioside , Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside, rubusoside, other steviol glycosides found in the Stevia rebaudiana Bertoni plant and their mixtures, Luo Han Guo extract, mogrosides, syrup high fructose corn, corn syrup, inverted sugar, fructo-oligosaccharides, inulin, inulo-oligosaccharides, coupling sugar, malto-oligosaccharides, maltodextrins, corn syrup solids, glucose, maltose, sucrose, lactose, aspartame, saccharine, sucralose, sugar alcohols, and a combination of these.
    18. Flavor composition, CHARACTERIZED by the fact that it comprises a highly purified stevia glycosyl composition produced by the process as defined in claim 1, and an additional flavoring agent selected from the group consisting of: lemon, orange, fruit, banana, grape, pear, pineapple, mango, bitter almond, cola, cinnamon, sugar, cotton candy, vanilla, and a combination of these.
    19. Food ingredient, CHARACTERIZED by the fact that it comprises a highly purified glycosyl stevia composition produced by the process as defined
    3. Process according to claim 2, in which it is characterized by the fact that the mixture of α-amylase and CGTase contains about 0.05 - 0.1 KNU of α-amylase per one unit of CGTase.
    [4]
    4/4 defined in claim 1 and an additional food ingredient selected from the group consisting of: acidulants, organic acids and amino acids, coloring agents, bulking agents, modified starches, gums, texturizers, preservatives, antioxidants, emulsifiers, stabilizers, thickeners, gelling agents, and a combination of these.
    4. Process according to claim 1, CHARACTERIZED by the fact that the weight of the added steviol glycosides is approximately equal to that of the starch used to make the first liquefied starch suspension.
    5. Process according to claim 1, CHARACTERIZED by the fact that the added steviol glycosides are selected from the group consisting of stevioside, Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside, rubusoside, as well as other steviol glycosides found in the Stevia rebaudiana Bertoni plant and their mixtures.
    6. Process according to claim 1, CHARACTERIZED by the fact that the weight of the first dry stevialy glycosyl composition added is almost equal to that of the starch used to make the second liquefied starch suspension.
    7. Process according to claim 1, CHARACTERIZED by the fact that the first dry stevia glycosyl composition comprises stevioside, Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, dulcoside A, steviolbioside, rubusoside and its α-1,4-glycosyl derivatives with up to nine α-1,4-glycosyl residues.
    8. Process, according to claim 1, CHARACTERIZED by the fact that CGTase is produced by cultures of Bacillus stearothemophilus.
    9. Process according to claim 1, CHARACTERIZED by the fact that CGTase is added to the amount of about 0.2 - 4 units per gram of solids.
    10. Process according to claim 1, CHARACTERIZED by the fact that CGTase is added to the amount of about 0.5 - 1.2 units per gram of solids.
    11. Process, according to claim 1, CHARACTERIZED by the fact that the decolorization is carried out using activated carbon.
    12. Process, according to claim 1, CHARACTERIZED by the fact that the
    [5]
    5 20. Food, drink, cosmetic or pharmaceutical product, CHARACTERIZED by the fact that it comprises a highly purified stevia glycosyl composition produced by the process as defined in claim 1.
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    法律状态:
    2017-11-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2018-07-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-08-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/05/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/05/2011, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/029,263|US8257948B1|2011-02-17|2011-02-17|Method of preparing alpha-glucosyl Stevia composition|
    US13/074,179|US8318459B2|2011-02-17|2011-03-29|Glucosyl stevia composition|
    PCT/US2011/035173|WO2012112180A1|2011-02-17|2011-05-04|Glucosyl stevia composition|
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