CN1088714C - Polymerization of mono- and disaccharides using low levels of polycarboxylic acids - Google Patents
Polymerization of mono- and disaccharides using low levels of polycarboxylic acids Download PDFInfo
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- CN1088714C CN1088714C CN98803480A CN98803480A CN1088714C CN 1088714 C CN1088714 C CN 1088714C CN 98803480 A CN98803480 A CN 98803480A CN 98803480 A CN98803480 A CN 98803480A CN 1088714 C CN1088714 C CN 1088714C
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract
Superior quality, clean-tasting food grade polydextrose is prepared by reacting glucose or glucose-containing materials such as hydrolyzed starch with a polyol such as sorbitol in the presence of low levels of a polycarboxylic acid such as citric acid. In one embodiment, polydextrose is prepared by reacting glucose or glucose-containing materials such as hydrolyzed starch with a polyol such as sorbitol in the presence of low levels, i.e., from about 0.03% to about 0.1% citric acid at a temperature of from about 145 to about 185 C., preferably from about 150 C. to about 160 C. Because of the low levels of catalyst used in preferred embodiments, minimal or no off-flavors and little color are formed during the course of the reaction, but the product may be purified using ion exchange, membrane filtration, or carbon treatment, or further modified by hydrogenation if desired for certain applications.
Description
Technical field
The application relates to the glucose that uses a small amount of polycarboxylic acid such as citric acid and carry out and the polymerization of other monose, obtains being particularly suitable for the Edible material that food uses.
Along with the human consumer to healthy, low calorie food goods growth of requirement, polymeric glucide such as dextrosan (polydextrose) have been widely used as the substitute of traditional sweeting agent, flour and other starch in the food formulations in recent years, and are widely used as fat restraining agent.For example, the reduction of caloric density is significant in the food article that uses dextrosan, this is because dextrosan only discharges the energy of about 1 kilocalorie/gram, it is equivalent to about 25% dextrose equivalent value and 11% fat value (Figdor, S.K. and Bianchine, J.R., J.Agric.Food Chem.1983,31:389-393).And, dextrosan is a kind of tasteless, dry weighting agent, can bring mouthfeel, quality and the palatability of higher calorie of food that carbohydrate brings to food, not influence the utilization of the VITAMIN, mineral substance or the indispensable amino acid that have disturbed some other sugar and fat-replacer use.In addition, in tooth test, dextrosan can not promote the formation of carious tooth or spot, so it can be used on and reduces in the candy that carious tooth generates etc.In food article, use dextrosan and relevant glycan class to substitute high calorie ingredients with all or part of, and also be used to increase artificial sweetening agent and substitute sugar, make dietary food product can keep its tempting physical appearance, also the quality and the nutritive value of food had contribution simultaneously.(summary of dextrosan, referring to Murray, P.R., in Birch, G.G.and Lindley, M.G., eds., Low-Calorie Products, Elsevier Applied Science, NewYork,, the 7th chapter, 84-100 page or leaf in 1988.)
Dextrosan water miscible, high collateralization has been widely used as weighting agent, formulation adjuvant, wetting Agent for Printing Inks and quality toughener at present, and range of application is in daily freezing dairy products such as ice-creams, ice milk and other sweets; Bake in food such as cake, cooky and the flour system pastry; Bake in the temper; In rock sugar, candy, syrup, food topping (toppings), sauce, edible jelly, pudding, beverage and the chewing gum.
Background technology
The polymerization under the acidic catalyst condition of known glucose.For example, Mora is at United States Patent (USP) 2,719, described the preparation of side chain carbohydrate polymer in 179.His method relate to-80 ℃-110 ℃, a kind of Louis silk acid catalyst in the presence of, the mixture of a kind of sugar or carbohydrate is remained in inert solvent or the thinner.He advises using spirit of salt, phosphoric acid, phosphorous acid, sulfuric acid, aluminum chloride, zinc chloride, tin chloride, boron trifluoride, butter of antimony or tosic acid to implement its invention, but has only used spirit of salt to make the dextrose polymerization in his embodiment.
Under acidity, hot conditions, carbohydrate, particularly monose easily carry out various reactions, comprise hydrolysis, dehydration, decomposition and polyreaction.Be easy to produce the color of yellow to brown and the product of caramel class smell is the complex mixture of anhydrosugar, hydroxymethylfurfural and other furan compound, levulinic acid, formic acid, polymer soluble, insoluble humin substances.These reactions for example, are disclosed in the TheCarbohydrates of W.Pigman, Chemistry, Biochemistry and Physiology (Academic Press, NewYork, 1957,57-60 page or leaf); W.Pigman and D.Horton, The Carbohydrates, Chemistryand Biochemistry (Academic Press, New York, 1972, the IA volume, 175-186 page or leaf and IIA volume, 95 pages); The Food Chemistry of O.R.Fennema (second edition, Marcel Dekker, Inc., New York, 1985,98 pages); With the Starch/starke of B.F.M.Kuster, in 42 volumes (1990, the 314-321 page or leaf).In the polymerization process of acid catalyzed carbohydrate, these reactions are restive, and object wherein is a kind of taste gentleness, light-colored polymkeric substance.
At United States Patent (USP) 2,436, in 967, Leuck has described a series of experiments, has compared the combination of sugar (preferably under molten state) employed various catalyzer of polymerization and various catalyzer in these experiments.He finds because basic salt owing to have the trend of decomposing or destroying dextrose, therefore can not work effectively, and as the catalyzer of polyreaction, neutral salt is more effective than acid.His report points out that usually, neutral salt is compared with acid or acid-salt, and the polymeric amount is bigger, and extent of polymerization is higher, and neutral salt also has an advantage: the color that its time per unit or per unit temperature form is lacked than the color of acid or acid-salt formation.
Rennhard has summarized at United States Patent (USP) 3,766, and disclosed use mineral acid promotes sugared polymerization to obtain the shortcoming of edible product in 165 and 3,876,794.The glycan class of using these acid catalysts to obtain from the component part list or the disaccharides of glycan class is normally dark, and peculiar smell is arranged.Except that caramelize that is observed and/or brown, the sour reversed reaction product that mineral acid also can the catalysis reversed reaction, depolymerization, formation reduce forward reaction efficient.And, for food applications, must from the formed product of polyreaction, remove the unedible catalyzer that in preparation process, uses, solvent etc. basically fully.In some cases, this is impossible, for example when catalyzer and goods formation mixture.
Rennhard proposes available nonvolatile edible organic polycarboxylic acid replacement mineral acid in the production of edible glycan class.He tests the catalyzer and the linking agent that are used as in glucose and the maltose polyreaction in various these class acid, is to carry out under molten state, decompression if find reaction, can access best product.If he finds that he introduces a kind of edible polyvalent alcohol such as sorbyl alcohol in sugar-carboxylic acid reaction mixture before the polymerization condensation reaction, can obtain excellent product.In addition, he also points out, by adjusting concentration, duration of the reaction, the temperature of reaction of initial acid, can simultaneously or separately obtain two class poly-dextroses and poly-maltose, and is soluble and insoluble.
Rennhard uses the food grade citric acid to prepare dextrosan finally to be become and is a kind ofly thought safe method (21 C.F.R. § 172.841) by Food andDrug Administration.But this method has its limitation for the required food-grade material of production.In order to make polymerization reach acceptable degree, use citric acid usually at least about 1% weight.Use the dextrosan of this tittle preparation to have some bitter tastes a little, this has limited its application in many food articles, and therefore many disclosed afterwards contents all are devoted to improve on taste.In the United States Patent (USP) 4,622,233 of Torres, for example pass through with a kind of solvent and a kind of acceptable SYNTHETIC OPTICAL WHITNER processing in food, to remove anhydroglucose (thinking that it has brought bitter taste), other impurity and some colors in the dextrosan.People's such as people such as Bunick and Luo United States Patent (USP) 4,948,596 and United States Patent (USP) 4,956,458 disclose respectively by solvent extraction and reverse osmosis and the purifying dextrosan.People's such as Guzek United States Patent (USP) 5,645,647 and 5,667,593 have disclosed the ion-exchange techniques of purifying dextrosan, and adopted combining citric acid is removed to the method for measuring below the 0.3mol%.Color, local flavor with improvement, and reduced with reactive dextrosan of food composition reaction and prepared (people's such as Borden United States Patent (USP) 5 to remove reduction glucose group by this polymeric articles of hydrogenation with amine functional group, 601,863).
Because the human consumer just more and more pays close attention to the F﹠B goods of minimizing and low calory, therefore it is desirable to alternative method, be used for the food-grade dextrosan that uses other method production performance good more economically.
Summary of the invention
The purpose of this invention is to provide a kind of improving one's methods of food-grade dextrosan that prepare, particularly a kind of method of using a spot of polycarboxylic acid to prepare the edible dextrosan.
The present invention further and more specifically purpose provides a kind of method of using very small amount of citric acid production edible dextrosan.
Another object of the present invention is the method that dextrosan and other glycan class modification and/or the purifying of a small amount of polycarboxylic acid Preparation of Catalyst of employing are provided in some embodiments.
These and other purpose of the present invention is realized by the present invention of the method for the glycan class that preparation height collateralization is provided, the glycan class of its camber collateralization is by at a kind of polyvalent alcohol such as sorbyl alcohol, glycerine, tetrahydroxybutane, Xylitol, mannitol, under the existence of melampyrum or its mixture, and in the presence of the polycarboxylic acid catalyzer of capacity, with a kind of sugar such as maltose, glucose or the material such as the hydrolyzed starch that contain glucose react, formation is suitable for eating (promptly, present light colour and a spot of peculiar smell) glycan, wherein the consumption of polyvalent alcohol is typically about 5-20%.In most of embodiments, method of the present invention has adopted about 0.001%-0.3%, the polycarboxylic acid catalyzer of preferred about 0.04%-0.1%, as citric acid, toxilic acid, oxysuccinic acid, pentanedioic acid, xitix, erythric acid (erythorbic acid), fumaric acid, tartrate, succsinic acid, hexanodioic acid, methylene-succinic acid or terephthalic acid, or the acid anhydrides of a kind of acid anhydrides such as toxilic acid, succsinic acid, hexanodioic acid or methylene-succinic acid, or the mixture of these acid and/or acid anhydrides.In one embodiment, catalyzer accounts for about 0.04%-0.10% of Citric acid weight.The product of Xing Chenging can be neutralized like this, further handle and purifying with ion-exchange, membrane filtration, exciusion chromatography, enzyme processing and/or carbon, and/or by the hydrogenation modification.In some embodiments, the ion-exchange purification step relates to the use of basic anion exchange or mixed bed resin.
Detailed Description Of The Invention
Basis of the present invention is to find that the food-grade dextrosan with ideal behavior can use a spot of polycarboxylic acid Preparation of Catalyst, and the product that obtains in some embodiments has the taste characteristic of the conventional dextrosan that the organic acid of the same race that is better than using higher amount makes.
In the embodiment of this invention, edible glycan class is following making: a kind of polyvalent alcohol and a kind of sugar or sacchariferous material are reacted in the presence of a kind of polycarboxylic acid or a kind of polycarboxylic acid mixture make.Polyvalent alcohol includes, but not limited to sorbyl alcohol, glycerine, tetrahydroxybutane, Xylitol, mannitol, melampyrum and composition thereof; Preferred in some embodiments sorbyl alcohol.Adopt anhydrous, hydration or a kind of polyvalent alcohol of aqueous solution form or the mixture of polyvalent alcohol in the typical embodiment.In reaction mixture, the consumption of polyvalent alcohol is generally about 5-20wt%, preferably about 5-15wt%.The usage quantity of polyvalent alcohol is about 8-12wt% in some embodiments.(unless stated otherwise, all per-cent that herein provides all is meant weight percent, and they are based on the weight of described particular stage.)
Steamed bun stuffed with sugar is drawn together glucose, maltose, other monose, the material that contains glucose and maltose such as hydrolyzed starch and composition thereof.In typical embodiment, this sugar is anhydrous, hydration or aqueous solution form.Advantage of the present invention is to obtain having the glycan class of different qualities slightly by changing sugared composition.At this used term poly-dextrose, dextrosan, poly-maltose and glycan is that to be used for naming wherein most of monomer segment be glucose, maltose or other sugared polymeric material, and some glucose wherein, maltose or other sugar moieties are by the polymeric material from the partial esterification in the polymerization activator.
In the embodiment of this invention, sugar and polyvalent alcohol are to react in the presence of polycarboxylic acid or its mixture, and wherein the amount of polycarboxylic acid or its mixture should be enough to form the glycan that is suitable for food applications, promptly have the product of light colour and a small amount of peculiar smell.Typically, the amount of catalyzer is about 0.001%-0.3% weight, the acid or the sour mixture of preferably about 0.05%-0.1% weight.For example, used the citric acid of about 0.03%-0.1% weight in one embodiment.When being higher than best acid concentration, reaction mixture can generate the product that has excessive color and peculiar smell usually; Use might not reach the acceptable polymerization degree under the optimum concn being lower than.Best acid concentration also has the advantage that makes product contain minimum catalyzer, its elimination or simplified further purification step.
The polycarboxylic acid that the present invention uses is preferably non-volatile, edible, includes but not limited to: citric acid, toxilic acid, oxysuccinic acid, pentanedioic acid, xitix, erythric acid, fumaric acid, tartrate, succsinic acid, hexanodioic acid, methylene-succinic acid and/or terephthalic acid or its mixture.Perhaps, can use the acid anhydrides of a kind of acid anhydrides such as toxilic acid, succsinic acid, hexanodioic acid and/or methylene-succinic acid, or these acid anhydrides mixture each other, perhaps the mixture of itself and polyprotonic acid.Used citric acid in one embodiment.
Preferred use minimum amount, because the product of gained does not need to be further purified like this, but this amount should be enough to promote the carrying out that react.Surprisingly, found that low-down sour consumption is manipulable, for example, 1% the amount of being lower than has been used in the production of most industrial dextrosan at present.The speed of reaction of using this tittle to obtain is an acceptable, and it is minimum that the acidity of dark colour, peculiar smell, product is reduced to, and as required, product can need not purifying and directly use in the food.As the above mentioned, the amount of about 0.05%-0.1% is particularly preferred.Perhaps, utilize the dextrosan of higher amount preparation can use ion-exchange, membrane filtration or carbon to handle purifying.
Reaction is normally carried out under anhydrous molten state.Dried atomizing glucose or maltose for example, mix with the acid of appropriate amount, and reactant heats under reduced pressure.In the embodiment of this invention, reaction duration and temperature of reaction are the reaction parameters that is mutually related.Preferred temperature of reaction is about 120 ℃-200 ℃, preferably about 130-170 ℃, and more preferably from about 150-160 ℃.The precise temp of anhydrous melt polymerization depends on the initial ratio, reaction times of glucose, maltose or other sugar and used acid and required solvable glycan class and the ratio of soluble crosslinked glycan class in the finished product.
In addition, reactant can be hydration when initial, perhaps in aqueous solution.In this case, water is normally removed from reaction mixture by the method for underpressure distillation, to promote the carrying out of polyreaction.
Heat exposure (reaction times and temperature) used in the process of glycan class produced according to the present invention should be lacked as much as possible, because variable color, caramelize and degraded meeting increase along with the growth that is exposed to the pyritous time.But,, finish the required time decreased of polyreaction basically fortunately along with the increase of polymeric reaction temperature.
Preferred pressure is no more than about 300mmHg, and for example about 10
-5To 100-300mmHg, this can obtain by using vacuum pump, steam jet atomizer, vent fan or alternate manner.Vacuum is to be used for getting rid of air in the polyreaction, to remove the water that discharges in water in the dewatering and the polyreaction.The eliminating of air also makes the decomposition of the glycan class that forms in the polyreaction and fades reduces to minimum.Also can remove air by logical nitrogen.
The reaction product that forms is a glycan, as poly-maltose or dextrosan." dextrosan " is meant as the acid of catalyzer with in the presence of as the polyvalent alcohol of softening agent and end capping agent, the glucose that thermopolymerization obtains.Dextrosan is water miscible, the random bonded condensation polymer of glucose, contains a spot ofly in conjunction with sorbyl alcohol, if use citric acid as catalyzer, is citric acid.Dextrosan is whole basically to be made up of the glucose polymer of random crosslinking, and described polymkeric substance has various types of glycosidic links, wherein mainly is the 1-6 key, and it comprises some sorbyl alcohol end groups.Except that polymkeric substance itself, it also comprises the initiator and the reaction product thereof of small portion of residual.
After reaction is finished, can use a spot of alkali neutralization reaction mixture.Although advantage of the present invention is only to have used a spot of acid, can not need further purifying so in some embodiments, in and dextrosan or poly-maltose for some application, be ideal, no matter employed acid catalyst amount how few.For example, when poly-dextrose was used in the dietary food product that comprises full milk, excessive acid can make milk rotten.Neutralization can be finished by the carbonate or the oxyhydroxide that add alkaline matter such as potassium, sodium, calcium or magnesium in the aqueous solution of glycan or glycan.Material with poly-dextrose or poly-maltose during other can be used for comprises: L-Methionin, D-glycosamine, N-methylglucosamine and ammonium hydroxide.Other tart method that reduces poly-dextrose or poly-maltose solution is dialysis, ion-exchange and reverse osmosis.
The glycan that forms can use ion-exchange, membrane filtration, exciusion chromatography, carbon processing, enzyme processing, bleaching, solvent extraction etc. or more than one method purifying.From the angle of economy, preferably only adopt a kind of processing as handling with anionresin or mixed bed resin.Soluble poly-dextrose and poly-maltose for example, can contact with activated carbon or charcoal by the aqueous solution with glycan and decolour.Glycan also can be with ethanol or methanol extraction.Perhaps, can bleach glycan.For example, (for example, every gram dextrosan uses 10mg H can to use the hydrogen peroxide bleaching dextrosan
2O
2) or dioxide peroxide (for example, 0.5 milligram of ClO of every gram dextrosan use
2).
In some embodiments, preferably adopt ion-exchange purification, include, but not limited to dextrosan is made slurry with resin or resin compound, perhaps by dextrosan solution is passed through resin column.Preferred resin comprises anionite-exchange resin (or weakly alkaline, or strong basicity), Zeo-karb or comprise anionite-exchange resin and the mixed bed resin of Zeo-karb.Usually, for ion-exchange purification, the concentration range of dextrosan is about 10-70%, and temperature is about 10-80 ℃, flow velocity be about 0.1-10 bed volume/hour, pressure is about 1-10 normal atmosphere.For some resins, need be lower than chemistry or the physical decomposition of the upper limit to avoid resin of the temperature and pressure of above-mentioned restriction.Preferred resin is a resin used in the ion-exchange purification that carries out under room temperature and barometric point.Ion exchange resin treatment has been removed acid catalyst, some colored byproducts and some peculiar smell.
In some embodiments, the ion exchange treatment of the low acid catalyzed dextrosan of consumption is brought and is not wished the special sense characteristic that exists than low degree.Because the known bitter taste of removing in the dextrosan that uses the higher amount Preparation of Catalyst has importance, so the reduction of the bitter taste of the catalytic dextrosan of being studied of small amount of acid is noticeable especially.An advantage of the invention is that the prepared according to the methods of the invention dextrosan can provide the product with gentle taste and light colour.Another advantage of the present invention is to use weakly alkaline anionite-exchange resin method of purification purifying dextrosan of the present invention, for example provides a kind of and has compared the product that tart flavour reduces with the dextrosan for preparing with traditional method.
Glycan prepared according to the methods of the invention can be by further modification.Illustrate that as above-mentioned they can be used to bleach the reagent bleaching of powder with Textone, hydrogen peroxide and other.Perhaps, they can utilize the method hydrogenation among the WO92/14761 that had mentioned.Usually, this relates to and utilizes continuously or interrupter method is exposed to dextrosan in the hydrogen under the temperature and pressure of the existence of hydrogenation catalyst, rising.For example, under the pressure of about 1000-2500 pound/square inch, can be in the presence of Raney nickel, about 100-160 ℃ of reaction about 30 minutes to about 6 hours with the aqueous solution of the dextrosan of 30%-60%.Normally the dextrosan solution after the hydrogenation is handled to remove dissolved nickel by Zeo-karb then.
Perhaps, dextrosan can be reduced with the hydride donor.For example, dextrosan prepared in accordance with the present invention can be about in the aqueous solution of 9-12 at the pH of 30%-60%, under environmental stress, about 5-80 ℃, utilize sodium borohydride and POTASSIUM BOROHYDRIDE to reduce about 30 minutes-12 hours as the hydride donor.Use any method, for some purpose, dextrosan is improved, because it does not have to cause the reactivity reduction group of not wishing the color that has and bitter taste basically.
As a further purification step, in some embodiments, the present invention's dextrosan unmodified or modification can be handled to improve its color, colour stability, taste, viscosity, stability etc. with enzyme, and these have been disclosed in the USP 5 of Duflot, 424,418,5,493,014 and 5,573, in 794 and the Can.Pat.No.2 of Caboche, 086,207.In typical embodiment, utilize various bacteriums or fungi Glycosylase or oxidasic specificity, perhaps come the preferential key that decomposes in the undesired side reaction product that in the process of polyreaction, forms, perhaps be used for removing the product of undesired small molecular weight.Typical enzyme purification is handled and is related to: enzyme is joined in the glycan product solution, is incubated for some time then, perhaps with the solution of glycan product with contact attached to the enzyme on the carrier.Useful enzyme includes but not limited to: glucose oxidase, amylase, β-glucosidase, starch glucosidase and their mixture.
The molecular-weight average of the preferred dextrosan of prepared according to the methods of the invention is about 1000-18000, and the taste gentleness does not have peculiar smell yet.In some embodiments, molecular-weight average is about 1500.The glucose content of preferred dextrosan prepared in accordance with the present invention is lower than about 4.0%, preferably be lower than about 3.5%, the content of sorbyl alcohol is less than or equal to about 3%, (the American Public HealthAssociation of APHA, APHA) color is 300 or lower, preferred about 200 or lower.The glucose content of the preferred especially dextrosan of the present invention's preparation is about 3% or lower, and the APHA color is about 150 or lower.Below provided embodiment, comprised that those APHA colors are about 100 dextrosan.
The amount that an advantage of the invention is ratio, reaction times, temperature, pressure and acid catalyst that the polymerization degree and reaction kinetics can be by changing reactant is controlled.The best amount that is used to obtain taste gentleness, colourless substantially dextrosan provides in the above.Comparative example given below has shown the preparation under different reaction conditionss.
Another advantage of the present invention is: because the amount of the catalyzer that consumes is low, and catalyzer the charge is small, so entire method is economical, and provide the dextrosan that does not need to be further purified step.Prepared dextrosan is with the product that uses other Preparation of Catalyst or use the acid of the same race of higher amount or the product of other Preparation of Catalyst to compare, the more shallow and peculiar smell reduction of color.In fact, in some embodiments, to such an extent as to the very low product that utilizes this method to form of the amount of acid need not neutralize or other purification step just can use.
The taste that it is dextrosan prepared in accordance with the present invention that the present invention also has an advantage is better than the taste with the dextrosan of relatively large acid preparation.For example, in the research that following embodiment part is carried out, use 20% dextrosan solution of 0.05-0.1% citric acid Preparation of Catalyst to have improved sweet taste according to implementation method of the present invention, and peculiar smell (for example tart flavour, bitter taste, astringent taste, chemistry flavor, corrode/burn etc.) is lower than the peculiar smell of the comparative solution of the dextrosan that contains the preparation of traditional use 1% citric acid." yellow cake " flavor (vanilla and creamy taste etc.) of the yellow cake that the dextrosan that utilizes the 0.05-0.1% citric acid to prepare is made is higher than the analog value of the cake that utilizes 1% citric acid-dextrosan preparation.Provide information more specifically below.
Though do not wish to be bound by theory, the raising that perceives of believing the desired taste performance of cake can be to reduce to be used as the food acids of catalyzer or the result who covers of its reaction product.
Embodiment
Following embodiment is used for further explaining the present invention, but says from which angle and should not be seen as limitation of the present invention.Unless otherwise indicated, all umbers and per-cent all are meant weight ratio, and based on the described process segment, color in 10% aqueous solution is according to the standard recording of APHA (APHA), wherein 0 representative is colourless, and molecular weight ranges utilizes high performance liquid chromatography (HPLC) to measure.Taste utilizes so-called sensory test (hedonic test) reflection, a kind of ordinary method of testing the food acceptability.14 people's taste evaluation group has been adopted in this test.It is a kind of direct Receptive test, and the evaluation group membership needn't need empirical personnel, but has used housebroken evaluation group membership in the test result of this paper.Give the evaluation group membership the numbered Receptive sample of evaluation that needs, evaluation group membership's acceptability is divided into the 1-9 grade; Also allow the evaluation group membership that other comment is provided simultaneously.In the common contrast test that adopts of the present invention, more paired side by side numbered samples, a dextrosan that contains conventional usefulness 1% citric acid preparation, another contains the dextrosan that the present invention uses 0.05-0.1% citric acid Preparation of Catalyst.
Embodiment 1 (contrast)
Use the dextrosan of 1% citric acid as Preparation of Catalyst
With the mixture fusion of 445 gram dextrose monohydrates and 50 gram sorbyl alcohols, and under partial vacuum, stirring, be heated to 132 ℃, add the solution of 5 gram citric acids in 10 ml waters.Continue again to stir, heated 22 minutes.The outlet temperature of reaction mixture is 165 ℃.Product contains 3.1% remaining glucose, and the APHA color in 10% aqueous solution is 100.
Embodiment 2
Use the dextrosan of 0.5% citric acid as Preparation of Catalyst
With the mixture fusion of 267 gram dextrose monohydrates and 30 gram sorbyl alcohols, and be heated to 132 ℃, add the solution of 1.5 gram citric acids in 5 ml waters, the temperature of reaction mixture is elevated to 152 ℃ in partial vacuum, under stirring.Stirred 10 minutes partial vacuum, 152-174 ℃ following a continuation.Product contains 2.6% glucose, and the APHA color in 10% aqueous solution is less than 100.
Embodiment 3
Use the dextrosan of 0.3% citric acid as Preparation of Catalyst
With the mixture fusion of 267 gram dextrose monohydrates and 30 gram sorbyl alcohols, and be heated to 130 ℃, add the solution of 0.9 gram citric acid in 5 ml waters, the temperature of reaction mixture is elevated to 152 ℃ in partial vacuum, under stirring.Stirred 20 minutes partial vacuum, 152-190 ℃ following a continuation.Product contains 1.2% glucose, and the APHA color in 10% aqueous solution is 175.
Embodiment 4
Use the dextrosan of 0.1% citric acid as Preparation of Catalyst
With the mixture fusion of 267 gram dextrose monohydrates and 30 gram sorbyl alcohols, and be heated to 130 ℃, add the solution of 0.3 gram citric acid in 5 ml waters, the temperature of reaction mixture is elevated to 152 ℃ in partial vacuum, under stirring.Stirred 22 minutes partial vacuum, 152-188 ℃ following a continuation.Product contains 2.3% glucose, and the APHA color in 10% aqueous solution is 125.
Embodiment 5
Use the dextrosan of 0.05% citric acid as Preparation of Catalyst
With the mixtures of 267 gram dextrose monohydrates, pure and mild 50 ml waters of 30 Keshan pears in partial vacuum, stir under heating finish substantially up to the water distillation, add the solution of 0.15 gram citric acid in about 5 ml waters, the temperature of reaction mixture is risen to 152 ℃.Stirred 27 minutes partial vacuum, 152-182 ℃ following a continuation.Product contains 2.9% glucose, and the APHA color in 10% aqueous solution is 125.
Embodiment 6
The local flavor of the dextrosan of a small amount of citric acid preparation of traditional dextrosan and use is described the comparison of (FlavorProfiles)
Use two evaluation groups, every group of 14 well-trained assessment officers, go assessment: as embodiment 4 described methods of amplifying in proportion, use 20% solution of dextrosan of 0.1% citric acid preparation and 20% solution (a kind of commerical prod of ion-exchange purification of Litesse, by Cultor, Inc. uses 1% citric acid Catalyst Production) the local flavor situation.In research for the second time, the evaluation group membership has assessed 20% solution of the dextrosan that uses the preparation of 0.05% citric acid and 20% solution of Litesse.
In twice research, sample is at room temperature to offer the evaluation group membership with the form in 50 milliliters of plastic cups of numbering.Evaluation the group membership report out them the descriptive impression to following flavor characteristics (flavor attributes), be divided into the 1-9 grade, described local flavor is: sweet, sour, salty, bitter, puckery, peppery (bite)/scald (burn), metal, warm, cold, numb, fruity (fruit notes), flower flavor (floral notes), blue or green flavor (greennotes), cotton flavour of candy, fennel flavor, musty, caramelize flavor, chemically distinguish the flavor of, other, sweet aftertaste, artificial sweetening agent aftertaste and peculiar smell aftertaste (off-notes aftertaste).
Contain in the research first time of the solution of the dextrosan that uses the preparation of 0.1% citric acid at 20% litesse solution and 20% relatively, evaluation value on the following taste of 0.1% citric acid dextrosan is lower, tart flavour (the mean value of litesse=2.7, the mean value of 0.1% citric acid-dextrosan=2.0), fiber crops flavor (the mean value of litesse=2.0, the mean value of 0.1% citric acid-dextrosan=1.1), similar aspect other characteristic of assessing.Contain in the research second time of the solution of the dextrosan that uses the preparation of 0.05% citric acid at 20% litesse solution and 20% relatively, evaluation value on the following taste of 0.05% citric acid dextrosan is lower, tart flavour (the mean value of litesse=2.7, the mean value of 0.05% citric acid-dextrosan=1.6), Metallic Flavour (the mean value of litesse=2.5, the mean value of 0.05% citric acid-dextrosan=1.7), astringent taste (the mean value of litesse=3.0, the mean value of 0.05% citric acid-dextrosan=1.9), similar aspect other characteristic of assessing.In the latter's research, tart flavour and astringent taste all have evident difference, p＜0.05.
The solution of 20% the dextrosan that will use 1% citric acid Preparation of Catalyst and not use that ion-exchange chromatography is further purified and use the solution of 20% dextrosan (also not carrying out purifying) of 0.05% and 0.1% citric acid Preparation of Catalyst, the research of being carried out above repeating respectively.Compare with 20% solution of the dextrosan that uses the preparation of 1% citric acid, the assessed value of 20% solution on sweet taste and cotton flavour of candy of the dextrosan of use 0.05% and 0.1% citric acid preparation is higher, and be lower in the assessed value of peculiar smell (off-notes) (sour, bitter, puckery, peppery/aspects such as boiling hot, chemical flavor).Descriptive result's average number evaluation has showed the difference that sample room perceives, and the result is summarized as follows, and uses the abbreviation of PDX as dextrosan.
Research 1 research 2
1% citric acid-0.1% citric acid-1% citric acid-0.05% citric acid-
PDX PDX PDX PDX
Sweet taste 2.8 5.0 2.5 4.8
Tart flavour 6.3 2.0 5.5 1.2
Astringent taste 5.0 2.3 4.4 2.5
Bitter taste 3.4 1.8 2.5 1.6 peppery (bite)/boiling hot (burn) 3.0 1.4 2.3 1.2
Blue or green flavor 2.1 1.6 1.6 0.6
Cotton flavour of candy 0.7 1.8 0.8 1.9
Caramelize distinguishes the flavor of 1.0 1.5 1.2 2.2
Chemistry flavor 4.1 2.7 3.3 2.2
Sweet aftertaste 1.5 3.8 1.6 3.0 artificial sweetening agent aftertaste 1.8 3.8 1.9 2.6
Peculiar smell aftertaste 4.6 2.5 3.5 2.6
The result shows the dextrosan that some flavor characteristics of the dextrosan that uses a small amount of citric acid catalyzer (being 0.05-0.1%) preparation are better than using traditional method (promptly 1%) to prepare.
Embodiment 7
Contain the comparison of yellow cake with the yellow cake that contains the dextrosan that uses a small amount of citric acid preparation of traditional dextrosan
In this embodiment, containing the yellow cake that the dextrosan that uses the preparation of 1% citric acid makes compares with the yellow cake that the dextrosan of the usefulness 0.05% of using same recipe, same amount and the preparation of 0.1% citric acid is made respectively.
Allow evaluation group remove to assess every group cake sample according to method described in the embodiment 6 with 14 well-trained evaluation group memberships.The yellow cake that yellow cake that the dextrosan that is to use the preparation of 1% citric acid that compares is for the first time made and the dextrosan that uses the preparation of 0.1% citric acid are made.The yellow cake that yellow cake that the dextrosan that is to use the preparation of 1% citric acid that compares is for the second time made and the dextrosan that uses the preparation of 0.05% citric acid are made.Sample at room temperature offers the evaluation group membership with the form in 100 milliliters of plastic cups.The evaluation personnel assess following flavor characteristics with the rate range of 1-9: sweet, sour, salty, bitter, puckery, vanilla, really/flower flavor, diacetyl basic taste, the oily flavor of milk (Huang), milk/milk preparation flavor, egg flavor, flour/starch flavor, musty, other flavor, sweet aftertaste, artificial sweetening agent aftertaste and peculiar smell aftertaste.Simultaneously also assess physical property, comprised hardness, viscosity, elasticity, density and humidity.
Descriptive result's average number evaluation has showed the difference that perceives between cake sample, and the result is summarized as follows, and PDX writes a Chinese character in simplified form as dextrosan.
Research 1 research 2
1% citric acid-0.1% citric acid-1% citric acid-0.05% citric acid-
PDX PDX PDX PDX tart flavour 1.6 1.0 2.0 1.6 fruit/flower flavor 1.6 2.1 1.6 2.0 diacetyls 3.4 4.0 2.9 3.4 creamy taste 1.7 2.1 1.7 2.1 eggs 3.0 2.9 2.7 3.4 peculiar smell aftertaste, 2.4 2.0 2.0 1.7 cake viscosity, 8.4 8.7 4.3 5.7 cake humidity 7.7 8.0 4.9 5.8 of distinguishing the flavor of
In addition, feel that cake sample also can compare.
From the local flavor test as can be seen, the cake that uses 0.05% citric acid-dextrosan to make has the assessed value of higher fruit/flower, cream and egg flavor, and this cake is assessed as and has higher " yellow cake " local flavor.And feel that the cake that the dextrosan that uses minimum (0.05%) citric acid Preparation of Catalyst makes is wetter, more tacky.
Embodiment 8
Contain the farm seasonings (ranch dressing) of traditional dextrosan and contain the comparison of the farm seasonings of the dextrosan that uses a small amount of citric acid preparation
According to the method described in the embodiment 7, adopt the farm seasonings to repeat above-mentioned comparison as a kind of food article.Carried out twice research, described according to embodiment 5, adopted every group of 14 well-trained members' evaluation group to be used for relatively using same recipe but the seasonings of different dextrosan samples.In research for the first time, the seasonings that relatively uses seasonings that the dextrosan of 1% citric acid Preparation of Catalyst makes and the dextrosan that uses 0.1% citric acid Preparation of Catalyst to make.In studying for the second time, the seasonings that the dextrosan of seasonings that the dextrosan that relatively uses 1% citric acid to prepare is made and the preparation of use 0.05% citric acid is made.
The assessment following properties, be expressed as the grade of 1-9, comprise the aftertaste of taste (cultured notes), seasoning fragrance (spices), onion/garlicky, musty, peculiar smell, other flavor of sweet, sour, salty, MSG sensation, bitter, puckery, hot/as to scald, milk flavor (dairy notes), fermentation, whole local flavor, typically aftertaste, peculiar smell and mouthful cover flavor.Compare with 1% citric acid-dextrosan, perceive the farm seasonings sweet taste raising (4.6 to 4.0) that 0.05% citric acid-dextrosan is made.Though statistically see, difference is not very remarkable, and all other exhilarating flavor characteristics are improved in the dextrosan that uses a small amount of citric acid preparation.
The result shows that in some embodiments, the comparable dextrosan that is suitable for the food use can use obvious a spot of citric acid to obtain in process of production.
Above-mentioned explanation is to be used for purpose of explanation, is not to be used for limiting the present invention, is used for telling how those of ordinary skill in the art goes to implement the present invention.Be not intended to describe in detail those those of ordinary skills at this and reading all conspicuous variation and the changes that to accomplish on the basis of specification sheets of the present invention.But, be noted that all these variations and change all to be included in the appended scope of the present invention that limits.Claims will cover the claimed composition that can effectively satisfy purpose shown in the present and the step of random order, unless article specifically notes that opposite content comes.
Patent of being quoted and paper are all quoted in full in this manual, as a reference.
Claims (14)
1. method for preparing the edible glycan, comprise and to be selected from glucose, other monose, sugar of hydrolyzed starch and composition thereof and 5-20% weight are selected from sorbyl alcohol, glycerine, tetrahydroxybutane, Xylitol, mannitol, the polyvalent alcohol of melampyrum and composition thereof is at the citric acid that is selected from of 0.001-0.3% weight, toxilic acid, oxysuccinic acid, pentanedioic acid, fumaric acid, tartrate, succsinic acid, hexanodioic acid, methylene-succinic acid, terephthalic acid, maleic anhydride, succinyl oxide, adipic anhydride, under the polycarboxylic acid of itaconic anhydride and composition thereof or the existence of acid anhydrides, decompression reaction under anhydrous fused polymeric reaction condition.
2. according to the method for claim 1, it is to carry out in the presence of 0.03%-0.1% weight polycarboxylic acid or acid anhydrides.
3. according to the process of claim 1 wherein that polycarboxylic acid comprises citric acid.
4. according to the process of claim 1 wherein that polyvalent alcohol is a sorbyl alcohol, sugar is glucose.
5. according to the process of claim 1 wherein that reaction is what to carry out under 120-200 ℃ temperature.
6. according to the method for claim 5, wherein reaction is what to carry out under 130-170 ℃ temperature.
7. according to the process of claim 1 wherein that the pressure in the reaction process is no more than 300mmHg.
8. according to the method for claim 1, during it also comprises and the step of edible glycan.
9. according to the method for claim 1, also comprise and use the purification step that is selected from following method: ion-exchange, membrane filtration, size exclusion chromatography, carbon are handled, enzyme is handled and its combination.
10. according to the method for claim 1, also comprise the afterreaction hydrogenation of the dextrosan that forms in the reaction.
11. according to the process of claim 1 wherein that the edible glycan comprises with 10% weightaqueous solution serves as that the wherein colourless APHA's standard of 0 representative is used on the basis, color is 300 or is lower than 300 dextrosan.
12. according to the method for claim 11, wherein the edible glycan comprises with the 10wt% aqueous solution serving as that the wherein colourless APHA's standard of 0 representative is used on the basis, color is 200 or is lower than 200 dextrosan.
13. method according to claim 1, wherein polyvalent alcohol, sugar and edible polycarboxylic acid catalyzer are under 120-200 ℃ temperature, under decompression, react for some time less than 300mmHg, to obtain molecular-weight average is 1000-18,000, use the wherein colourless APHA's standard of 0 representative, color is 300 or is lower than 300 edible glycan.
14. according to the method for claim 13, wherein polyvalent alcohol is a sorbyl alcohol, sugar is glucose, and the edible glycan is a dextrosan.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82011597A | 1997-03-19 | 1997-03-19 | |
| US08/820,115 | 1997-03-19 | ||
| US4306798P | 1998-01-30 | 1998-01-30 | |
| US60/043,067 | 1998-01-30 |
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| CN1251109A CN1251109A (en) | 2000-04-19 |
| CN1088714C true CN1088714C (en) | 2002-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98803480A Expired - Lifetime CN1088714C (en) | 1997-03-19 | 1998-03-19 | Polymerization of mono- and disaccharides using low levels of polycarboxylic acids |
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| Country | Link |
|---|---|
| CN (1) | CN1088714C (en) |
| AU (1) | AU6571898A (en) |
| WO (1) | WO1998041544A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20040026136A (en) * | 2001-04-10 | 2004-03-27 | 다니스코 유에스에이 인코포레이티드 | Polymerization of mono and disaccharides with monocarboxylic acids and lactones |
| FI20021772A (en) * | 2002-10-04 | 2004-04-05 | Biotie Therapies Oyj | Novel carbohydrate compositions and process for their preparation |
| CN101824097B (en) * | 2010-03-29 | 2012-04-11 | 天津科技大学 | Method for producing polyglucose |
| CN101880298A (en) * | 2010-07-16 | 2010-11-10 | 天津科技大学 | Method for preparing food-grade xylooligosaccharide |
| CN101921344B (en) * | 2010-08-06 | 2012-05-23 | 西北师范大学 | Method for extracting polysaccharides from Lilium Brownii |
| CN101914166A (en) * | 2010-08-25 | 2010-12-15 | 吉林化工学院 | Technical method for decoloring and deproteinizing corn stigma polysaccharide |
| CN103740070B (en) * | 2014-01-15 | 2016-03-23 | 湖北金叶玉阳化纤有限公司 | A kind of sugar alcohol polydactyl acid copolymer material and pipe tobacco thereof |
| LT3285777T (en) | 2015-04-23 | 2021-11-25 | Kaleido Biosciences, Inc. | Glycan therapeutics and methods of treatment |
| CN111315388A (en) | 2017-11-03 | 2020-06-19 | 卡莱多生物科技有限公司 | Glycan formulations and methods of use for hyperammonemia |
| CN113056488B (en) * | 2018-08-21 | 2023-10-24 | Dsm营养产品有限责任公司 | Oligosaccharide compositions and methods of use thereof for reducing ammonia levels |
| CA3118909A1 (en) | 2018-11-08 | 2020-05-14 | Kaleido Biosciences, Inc. | Oligosaccharide compositions and methods of use thereof |
| CN114107041A (en) * | 2021-12-26 | 2022-03-01 | 浙江华康药业股份有限公司 | System and method for preparing erythritol and polydextrose by using corn starch |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3766165A (en) * | 1966-08-17 | 1973-10-16 | Pfizer | Polysaccharides and their preparation |
| FR2266742A1 (en) * | 1974-04-05 | 1975-10-31 | Pfizer | |
| US4376198A (en) * | 1980-01-11 | 1983-03-08 | Chimicasa Gmbh | Process for the manufacture of glucosylsorbitol |
| EP0380248A2 (en) * | 1989-01-26 | 1990-08-01 | Pfizer Inc. | Modified polydextrose and process therefor |
| EP0404227A2 (en) * | 1989-06-22 | 1990-12-27 | Coöperatieve Vereniging Suiker Unie U.A. | Process for the preparation of polysaccharide derivatives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5667593A (en) * | 1989-01-26 | 1997-09-16 | Cultor Ltd. | Modified polydextrose and process therefor |
| KR930001317B1 (en) * | 1990-04-19 | 1993-02-25 | 선일 포도당 주식회사 | Polydextrose and process therefor |
-
1998
- 1998-03-19 CN CN98803480A patent/CN1088714C/en not_active Expired - Lifetime
- 1998-03-19 WO PCT/US1998/005467 patent/WO1998041544A1/en active IP Right Grant
- 1998-03-19 AU AU65718/98A patent/AU6571898A/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3766165A (en) * | 1966-08-17 | 1973-10-16 | Pfizer | Polysaccharides and their preparation |
| FR2266742A1 (en) * | 1974-04-05 | 1975-10-31 | Pfizer | |
| US4376198A (en) * | 1980-01-11 | 1983-03-08 | Chimicasa Gmbh | Process for the manufacture of glucosylsorbitol |
| EP0380248A2 (en) * | 1989-01-26 | 1990-08-01 | Pfizer Inc. | Modified polydextrose and process therefor |
| EP0404227A2 (en) * | 1989-06-22 | 1990-12-27 | Coöperatieve Vereniging Suiker Unie U.A. | Process for the preparation of polysaccharide derivatives |
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| CN1251109A (en) | 2000-04-19 |
| WO1998041544A1 (en) | 1998-09-24 |
| AU6571898A (en) | 1998-10-12 |
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