DE2305494B2 - Process for the enzymatic production of starch hydrolysis products - Google Patents

Description

The invention relates to a process for the enzymatic production of starch hydrolysis products a degree of degradation expressed by the dextrose equivalent DE of 5 to 8%.

The production of starch degradation products with a low DE (range 5 to 25%) is known per se. Acid hydrolytic and enzymatic processes are used for the hydrolysis of all known types of starch, preferably waxy cereal starches. In one case of the reaction procedure for the production of starch hydrolyzate compositions with low DE, a starch that has been dissolved in an aqueous medium at a temperature above the gelatinization temperature of the starch in question is liquefied and by bacterial alpha-amylase at a temperature of less than 95 ⁰ C hydrolyzed to DE values between 5% and 25%. In another case of the reaction procedure for the production of highly concentrated dextrin solutions for the paper industry, a potato starch suspension is first broken down at a temperature below the gelatinization temperature with alpha-amylase at 59 ° C to such an extent that the suspension is above the gelatinization point when the temperature is subsequently increased assumes such a viscosity that it can be stirred. In a second degradation stage, the hydrolysis is then continued at around 75 to 80 ° C up to the desired final viscosity and the enzyme is inactivated by adding fermentation poisons, oxidizing agents or acids
The known processes lead to starch degradation products which form viscous solutions with water at concentrations above about 30% by mass, which are characterized by high stability against freeze-thawing and heating processes, high clarity, crystallization-inhibiting effect and the property that they are also in do not solidify like a gel in very high concentrations. Due to the lack of dimensional stability, such starch degradation products cannot be used as consistency carriers for certain food preparations.

It is also known that undegraded cereal starches dimensionally stable after gelatinization in water at a concentration of about 8 to 12% by mass Result in puddings that have gel-like properties. The same properties as cereal starches show potato starches that have been slightly modified by appropriate treatment with chemicals (so-called. Potato starch flour). Gel-like preparations can also be made from non-gel-forming starches, in particular waxy cereal starches, are obtained after being put into them by a chemical derivatization process functional groups are introduced.

The main disadvantage of the mentioned types of starches is that their gels made with water as Carriers or additives in foods and food

ij then preparations are not suitable when they are exposed to the influence of temperatures below the freezing and prolonged storage at room or refrigerator temperatures. Such gels and starch dispersions undergo irreversible transformations on freezing, and the starch is present as a water-insoluble, sponge-like mass after thawing. When storing such starch gels, e.g. B. as puddings or pastes, the high molecular weight starch components associate with the formation of hydrogen bonds, the consistency changing so that the gel hardens and repels water. The appearance and other sensory properties are adversely affected. All of the changes mentioned can go through

*> () Do not undo heating.

Further disadvantages of native starches are that their gel-like preparations very often have a typical, sticky-sticky texture and a characteristic, species-specific taste.

Such products are not suitable for use in such foods or food preparations where it is important that they retain their shape after painting and spraying. A additional disadvantage of the products mentioned results

bo is derived from the fact that after gel formation by heating no phase transformation can be achieved and thus the subsequent homogeneous incorporation of solid or dissolved ingredients, e.g. B. of salts, sugar, colorings, preservatives and others, largely

b5 sword or no longer possible.

In DE-OS 19 55 392 a two-stage process for degrading starch is described. A liquefaction stage at temperatures above 90 ^° C. follows

re-addition of the bacterial alpha-amylase Dextrination stage at temperatures between 65 ° and 85 ° C. The degradation products produced show in an aqueous medium, according to the task, no tendency to association, gelation or turbidity. A manufacture of thermoreversible Gels in an aqueous medium are not possible with the degradation products of DE-OS 19 55 392. The content of Degradation products with high molecular weight is pushed back by the procedure The after Products which can be manufactured using this known process therefore differ on the basis of their properties basically of those of the method according to the invention, such as may be mentioned. B. the formation of thermoreversible Gels, the content of high molecular weight degradation products, the optical absorption maxima the polysaccharide-iodine complexes.

The purpose of the invention is to address the deficiencies of the previously known strengths, To eliminate starch derivatives and starch hydrolysis products to the extent that such preparations are produced that form white, glossy, thermoreversible, tasteless gels with water, which are freeze-thaw-stable and whose consistency can be varied from pasty to cut-resistant

The invention is based on the task of developing a process according to which strengths, including low-substituted starch derivatives, enzymatically in different products Degree of degradation. These breakdown products must be largely free of D-glucose and maltose as well as smell and taste-intensive substances.

The inventive method for the enzymatic production of starch hydrolysis products from starch, which have a degree of degradation of 5 to 8%, expressed by the dextrose equivalent DE, by the action of starch-splitting bacterial alpha-amylase in water at a solids concentration of the suspension from 15 to 50% by mass and an optimal pH value for the enzyme as well as increased Temperature with subsequent inactivation of the bacterial alpha-amylase by further increasing the temperature, is characterized by the measures in the characterizing part of claim 1.

According to the invention, the degradation temperature is therefore initially kept at a level that is around 1 to 4 Celsius degrees below the start of the swelling temperature range, d. H. the incipient increase in consistency is, and the degradation is with increasing temperature up to the upper limit of the swelling temperature range of the starch granules continuously or with the introduction of one or more holding stages up to continued to dissolve all irreversible swollen starch granules. The degradation of the starch takes place within from 5 to 30 min.

By means of the measures according to the invention, the heterogeneous enzymatic hydrolysis is carried out in such a way that that part of the starch polysaccharides, namely the part in solution, is essentially due to the enzyme is broken down faster and more extensively than the other part of the starch polysaccharides, which is more solid Phase is located within the swollen grains. Because of these two different physical The enzymatic degradation leads to hydrolysis products with the desired state of the substrate Molecular size distribution, it must be noted that the character of this distribution is not subsequent by too long an incubation time at the actual temperature optimum of the bacterial alpha-amylase, the at high substrate concentrations between about 80 ° C • and 87 ° C is balanced again. That's why it is For the method according to the invention it is crucial that the enzyme is inactivated during heating Temperature range is passed quickly.

According to the invention, the reaction mixture is therefore to 95 for enzyme inactivation within 12 to 15 minutes Heated to 100 degrees Celsius and kept in this temperature range for 5 to 20 minutes.

The coagulable substances, preferably those in the tuber and root thicknesses, also flocculate Accompanying substances present protein substances as well as the enzyme protein, from and are, if necessary, after Addition of deodorizing and / or decolorizing substances, separated from the hydrolyzate in a manner known per se. This is either converted into a gel by cooling or converted into a dry product by dehydration. Dehydration is preferably carried out by Spray drying. Roller drying and freeze drying have also proven to be useful.

For the starch hydrolysis products to be produced according to the invention, tuber and root starches are included the potato starch is preferably suitable as a starting substrate, with starch concentrations of 25 to 30% by mass have proven to be particularly favorable. In addition, there are also those with low levels of substitution Starch derivatives whose functional groups are nutritionally harmless and which are can be degraded by alpha-amylases, preferably phosphate and acetyl starches, as the starting substrate usable. Starches pretreated differently can also be used, their swelling temperature range compared to untreated starches

j5 certain pre-treatment measures, preferably by artificial aging by means of heat-moisture treatment or by modifying the viscosity behavior by means of calcium or other ions, was changed.

The starch hydrolysis products prepared according to the invention can already be incorporated during manufacture Additions such as B. bring in nutrients and additives, foods, food preparations and enzymes. This is particularly important when small amounts of certain substances such as dyes, Preservatives, emulsifiers, stabilizers and others. are to be added to the starch hydrolysis products. Appropriately, such additives are added to the solutions before they are further worked up.

The starch hydrolysis products prepared according to the invention with a DE of 5 to 8% contain components which form complexes colored with iodine. In the case of produced from potato starch Stärkehydrolysenprodukt these complexes have at Jodnormalitäten of 4 ■ 10- ⁴ N in the wavelength region 530 to 550 nm has an absorption maximum which is shifted with the increase of the iodine concentration for smaller wavelengths.
The starch hydrolyzers produced according to the invention

Bad products with DE values of 5 to 8% are not hygroscopic and after dissolving in water depending on the concentration on cooling pasty to solid white glossy gels, if a certain concentration of preferably 15 to 40

μ mass% is reached. Below about 15 to 18 Mass-% pulpy consistencies develop.

A particular use of the starch hydrolysis products produced is based on the achievement of

impasto, spreadable, dimensionally stable masses with a consistency similar to common food fats such as butter, margarine or lard; included the dry matter content of aqueous preparations is adjusted to values between 25 and 30 mass%,

A considerable change in consistency occurs when the gels of the starch hydrolysis products prepared according to the invention are heated. The gels melt in the temperature range from 50 to 70 ^° C., resulting in optically clear, aqueous solutions (sols). When it cools down again, the solution solidifies again to form a gel.

The gels have the special property that they can be mixed with common food fats such as butter, Margarine and lard are completely and partially miscible with vegetable oils and also in this form show no phase separation when stored for long periods at room or refrigerator temperatures.

Due to the properties listed, the starch hydrolysis products are dry or with Prepared form for water, preferably in gel form, as carriers or additives for food and Food preparations can be used, if necessary with the addition of fats, fatty acids, medium-chain Triglycerides, protein, protein hydrolysates, amino acids, carbohydrates, salts, acids, dyes, Flavorings, vitamins, enzymes, hormones, emulsifiers, stabilizers, preservatives, ethanol i.a.

One area of application is based on the low hygroscopicity and the good solubility in water of the Starch hydrolysis products. They can be used advantageously as drying aids and carrier substances Use dehydration of sensitive substances, e.g. B. in the spray drying of spices, Instant beverages (coffee, tea, cocoa, fruit drinks), spices, flavors, enzymes as well as fruit and Vegetable homogenates or concentrates.

Other possible applications result from the use of the gels or the hydrolysis products as a thickener, stabilizer, body-giving and water-binding additives to puddles, cream dishes, Soups, sauces, coffee whiteners, ice cream mixes, fruit drinks, vegetable concentrates, Milk beverages, canned food and prepared meals. Advantages to be emphasized in this area of application are the freeze-thaw reversibility of the gels, which is important in the production of frozen food, as well their ability to melt with aqueous liquids in any proportion due to their meltability are miscible. This is i.a. when using starch hydrolysis products as an essential ingredient in sauces in canned fish, meat, vegetables and fruit, in which this is beneficial during sterilization escaping tissue water must be absorbed by the sauce without phase separation.

Additional areas of use for the starch hydrolysis products prepared according to the invention arise in that their aqueous preparations are miscible with protein substances by being concentrated in the gels Protein solutions such as egg yolks and egg whites can be incorporated by mixing or by being diluted in aqueous "protein solutions, e.g. milk, dry preparations of the starch hydrolysis products manufactured according to the invention dissolved and the mixtures can be brought to gel formation.

In many of the areas of application mentioned, it is of great application engineering importance that the Consistency of the gels against the influence of that required in numerous food preparations Additions of salts and acids is insensitive

The starch hydrolysis products prepared according to the invention are characterized by their taste neutrality and by their natural dietary fats approximate consistency and melting behavior in the mouth. They are similar to the natural spreads the gels according to the invention such that none

, o further additives for generating opacities and Shine are required. Due to these special properties, the gels according to the invention can be used as Fat substitutes are used wherever the fat is conventionally used as a consistency builder functions: in cake creams and fillings, toppings, mayonnaises and tartar sauce, cheese creams and others Cheese preparations, spreads, food pastes, Meat and sausage products and whipped creams. The use of these gels for the exchange of dietary fats or proteins in such products offers the technological advantage that the consistency Hand of the dry matter content to be set can be adapted to the desired application can. Furthermore, an improved consistency stability is achieved during storage at room, refrigerator and freezer temperatures.

In addition to these technological advantages, there is considerable value in the inventions Gels made therein.

that they offer comprehensive new possibilities for the preparation of reduced-fat and thus reduced-calorie foods Offer. The considerable reduction in calories is achieved by making the gels about 75% water contain, and that their dry matter consists of an easily digestible carbohydrate, the calorie content of which is only about half the size of fat.

The invention is to be explained in more detail using the following exemplary embodiments.

example 1

In a 1-1 three-necked flask are 270 g of potato starch (18.5% moisture) suspended in 630 ml of water and the pH adjusted to 7 using IN sodium hydroxide solution (Dry matter content of the suspension = 24.4% by mass). After adding 0.56 ml proteinase-free Bacterial alpha amylase with an activity of 58.6 KNE / g enzyme preparation (1 KNE unit = 1 kilo NOVO unit corresponds to 0.0189 conventional SKB units), which has a concentration of 0.172

so KNE / g starch dry substance is equivalent in the approach, the Reaction vessel with contents by means of a fiberglass heating mantle (220 V, 400 W, 3 heating levels) in two stages heated up:

a) heating the system at a heating rate from 0.9 degrees Celsius per minute (heating level 1) to 62 to 64 ° C;

b) further heating the system at a heating rate from about 4 degrees Celsius per minute (heating level 3) from 64 ° C to 100 ° C and Maintain this temperature for 15 min for complete inactivation of the enzyme and for coagulation of proteins.

In this program, the reaction time is the degradation in the heterogeneous phase (temperature range 59-70 ⁰ C) 8.2 min. The temperature range of 70 to 90 ° C (homogeneous phase) is passed through in 12 min.

The hydrolyzate obtained is then centrifuged to separate the protein by evaporation concentrated in vacuo to a dry matter content of about 50% by mass, poured into dishes, in dried, ground and sifted in a climatic cabinet with air circulation for 24 to 48 hours at 50 ° C. The starch hydrolysis product has a residual moisture of 8.2% and a DE value of 5.2%.

Example 2

In a 20-liter hanging vessel made of glass, 5.68 kg of potato starch (12.0% moisture) are mixed with 10.981 water suspended and the pH adjusted to 7 (dry sub- i> punched the suspension. = 30 mass%). To Addition of 9.28 ml protein-free bacterial alpha-amylase, corresponding to a concentration of 0.125 KN E / g starch dry substance in the approach, the Suspension with stirring (stirrer with a 120 mm: <i Sheet, 200 to 280 rpm) heated by direct introduction of steam according to the following program:

a) heating up to 59 ° C at a rate of 1.5 degrees Celsius per minute;

b) holding this temperature for 10 min;

c) heating to 63.5 ° C. within 3 minutes;

d) holding this temperature for 10 min;

e) heating to 90 ° C. at a rate of 1.4 degrees Celsius per minute;

f) Heating in a further 10 min to 100 ° C and holding this temperature for 20 min.

In this program, the reaction time is min during the degradation in the heterogeneous phase (temperature range 59-70 ° C) 28.4. The temperature range of 70 to 9O ⁰ C (homogeneous phase) is passed through in 15 min. The volume of the batch increases from the original 14.6 liters to 18.3 liters, and the dry matter content falls accordingly to 28.2% by mass. The hydrolyzate is filtered hot through a Dederon nettle filter cloth, concentrated in vacuo to a dry matter of 45 mass%, and on an attempt drum dryer (roller heating 220 V, 3.3 kW, 3 heat) at a roll temperature 115-125 ⁰ C dried at a feed rate of 30 ml / min. The starch hydrolysis product has a residual moisture content of 8.2%, a crude protein content of 0.1% and a DE value of 8.1%.

The starch hydrolysis products prepared according to Examples 1 and 2 give complexes colored in 0.1N hydrochloric acid with iodine-potassium iodide solution with the values given in the table for the parameters measured at two different iodine normalities for the wavelength of the absorption maximum (A _ma »in nm) and the maximum extinction coefficient (e _mM ), expressed as the extinction for 1 mg SHP in 100 ml iodine-potassium iodide solution with a molar iodide / iodine ratio of 1.5 with a layer thickness of the solution of 1 cm:

Starch hydrolysis product
according to

DE

Measurement when iodine normality is 4 · 10 " ³ N

/. max ί max

[nm] Measurement with iodine normality 4 · KT ⁴ N

/. max f m;

[nm]

example 1
Example 2

5.2

527 503 0.112
0.095

546

532

0.061
0.043

Example 3

In a beaker, 170 g of potato starch (15.6% moisture) with 328 ml of water are homogeneous Stir the suspension (dry matter content of the suspension 28.8% by mass), the pH using 2N sodium carbonate solution set to 7 and transferred to the measuring cup of a viscograph. After adding different ml amounts of bacterial alpha-amylase (see the table) will run the system at a rate of heating of 1.5 degrees Celsius per minute with the introduction of holding levels according to the following program heated, the consistency being registered as a function of time:

a) heating to 59 ° C;

b) constant temperature for 15min;

c) heating to 63.5 "C;

d) constant temperature for 5 min;

e) heating to 65 ° C .;

f) constant temperature for 5 min;

g) heating to 68 ° C .;

h) constant temperature for 5 min;
4i i) heating to 90 ° C .;

In this program, the reaction time is during the degradation in the heterogeneous phase (temperature range 59-70 ° C) 37.3 min. The temperature range of 70 to 90 ⁰ C (homogeneous phase) is passed through in 13 min.

The batch is transferred to a beaker, boiled for 15 min and, after cooling, placed in a refrigerator to form a gel. The table shows the consistency maxima achieved when using three different amounts of enzyme and the appearance of the sol obtained by heating the respective gel to 80.degree.

Amount of enzyme in viscograph units for the holding stages

[ml] 63.5 C 65.0 C 68.0 C

Appearance of the sol at 80 ° C

0.25
0.22
0.20

50
210 100

100 150 490 100 240 260

clear clear cloudy

In the example given, 0.20 ml of enzyme solution are required to obtain degradation products that able to form thermoreversible secondary valence gels.

The following are examples of gel formation and the use of the starch hydrolysis products prepared according to the invention:

Example 4

Gels are prepared with varying dry matter content by the corresponding amount of the dry product with a weighed amount of water with stirring and heating is performed in a water bath at 8O ⁰ C in a clear solution of the product prepared in Example 2 Stärkehydrolysenprodukte. To determine the gel strength, 70 ml of the solutions are poured into a Ridgclimeter beaker coated with silicone grease and stored at 4 ° C. for 24 h. By means of an automatic penetrometer (5 see) is the depth of penetration measured in mm using a standardized indenter (mass 10 g) and a predetermined penetration ■ '(maximum penetration depth 20 mm).

To determine the melting behavior,> 10 ml of the solutions with different dry matter content are poured into test tubes and the gel is formed in the refrigerator within 24 hours. The jars are placed individually in a spacious, heated at 8O ⁰ C water bath and the gel κι stirring with a thermometer caused to melt, whereby the change in consistency is observed. The melting point stated is the temperature at which the liquid phase is formed and the gel can be mixed. The clear point is given as the temperature at which the sol appears to be optically clear. The following table shows some gel properties depending on the dry matter content:

Dry matter example Consistency salary 13.8 pulpy 18.4 the same 23.0 pasty 27.5 the same 32.1 the same 36.7 cut resistant 41.3 the same 45.9 the same 5

Penetration depth of the Melting point Clear Standard body Point [mm] m [C] 20.0 _ 59 20.0 - 59 17.7 52 65 5.7 55 66 1.7 58 68 0.5 60 70 0.3 60 70 0 60 70

25 g of the starch hydrolysis product prepared according to Example 1, 0.5 g of common salt, 0.015 g of sodium benzoate and 0.085 g of benzoic acid are dissolved in 75 ml of water with gentle warming and, after cooling, 1 g of diacetyl-like butter flavor is added. As soon as the gel has formed in the refrigerator, 66 g margarine or butter or a mixture of these two fats are stirred in. This mass has the consistency of natural spreadable fats, can be spread in the same way at room or refrigerator temperature and does not release the water bound in the gel (approx. 53% by mass) when it is spread on bread. The fat content of this product is 32% by mass, it contains about 360 kcal / 100 g. By adding egg, sugar, flavor and coloring, the spread can be processed into various types of creams for baked goods and desserts.

Example 6

In 63 ml of water at 80 ⁰ C. 27 g of Stärkehydrolysenproduktes prepared according to Example 2 together with 50 g of sugar dissolved, various spices (vanillin, nutmeg cinnamon clove, cardamom, etc.) added thereto, and after cooling to about * 40 ° C with a Kakaobrei , consisting of 25 g de-oiled cocoa powder, 5 g butter and 60 ml milk mixed with a whisk. Forms in the refrigerator

A mushy, flowing mass is left out overnight, which can be used as a dessert, confectionery filling, cream for baked goods or can be used as a spread. The fat content of this chocolate mass is about 4% by mass, them contains about 209 kcal / 100 g.

Example 7

In a hornogenizer, 24.8 g sunflower oil, 15.1 g egg powder, 4.7 g spice vinegar, 3.0 g sugar, 3.0 g mustard, 225 g salt, 0.15 g sodium benzoate and 0.15 g Potassium sorbate mixed intensively and then 100 g of the hydrolyzate prepared according to Example 1 added with further homogenization. After training the additional valence gel in the refrigerator or at room temperature will make the mayonnaise firm Contains 17.2% by mass of fat and 272 kcal / 100 g.

Example 8

25 grams of cheese (Art Toll Enser) with a fat content of 252% and a 29.5% Proteinghalt of contact, together with 10 ml of water and 0.5 g of salt melting at 85 ° C and heated to complete melting at 50 ⁰ C cooled In this Temperature will be without

to further heating 35.5 g of a gel consisting of 25 g of starch hydrolysis product (prepared according to Example 1), 0.025 g of an emulsifier and 75 g of water are stirred in and the initially mushy, flowable mass is placed in a refrigerator. After 48 h the mass is spreadable.

b5 hig. It contains 83% fat and 173 kcal / 100 g.

fr- "t H

Claims (3)

Patent claims: • ΐ. Process for the enzymic production of starch hydrolysis products from starch, which have a degree of degradation of 5 to 8% expressed by the dextrose equivalent DE Effect of starch-splitting bacterial alpha-amylase in water at a solid concentration of the suspension from 15 to 50% by mass and an optimal pH value for the enzyme as well as increased Temperature with subsequent inactivation of the bacterial alpha-amylase by further increasing the temperature, characterized in that the degradation of the starch within 5 to 30 minutes with a continuous or gradual increase in Temperature takes place, after adding the bacterial alpha-amylase initially to a temperature is heated, which is 1 to 4 degrees Celsius below the range of the swelling temperature of each starch used, followed by heating up to the upper limit of the swelling temperature range takes place, the reaction mixture for enzyme inactivation within 12 to 15 min to 95 to 100 degrees Celsius is heated, is held in this temperature range for 5 to 20 minutes, whereupon the doing coagulating substances are separated and the hydrolyzate obtained either by cooling in a Gel is transferred or dried. 2. Modification of the method according to claim 1, characterized in that low-substituted, Nutritionally harmless, alpha-amylolytically degradable starch derivatives, preferably Phosphate and acetyl starches, or other pretreated starches, preferably artificially aged and / or starches modified with calcium or other ions. 3. Use of the starch hydrolysis products prepared according to claims 1 and 2 with water and fats mixed in spreadable and sprayable masses.