DE2305494C3 - Process for the enzymatic production of starch hydrolysis products - Google Patents

Description

The invention relates to a method for enzyme particles Manufacture of starch hydrolysis products with tinem expressed by the dextrose equivalent DE Degree of degradation from 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. applied. In one case of the reaction procedure for the production of starch hydrolyzate compositions with low DE, a starch which 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 ° C to DE 'values between 5% and 25% in a different case of the reaction procedure for the production of highly concentrated dextrin solutions for the paper industry, a potato starch suspension is initially at a temperature that is below the yeast temperature, with alpha-amylase at 59 ° C degraded to such an extent that, when the temperature is subsequently increased above the gelatinization point, the suspension assumes such a viscosity that it can be stirred. In a second reduction stage is then up to the desired final viscosity continued at about 75 to 80 ⁰ C and the hydrolysis the enzyme was inactivated by addition of Fermentgiften, oxidizers or acids.

The known processes lead to starch degradation products with water at concentrations above Form about 30% by mass of viscous solutions, soft due to high stability against freeze-thaw and Heating processes, high clarity, anti-crystallization Effect and characterized by the fact that they are also used in very high concentrations do not solidify like a gel. Due to the lack of dimensional stability, such starch degradation products are as Consistency carrier for certain food preparations not useable.

It is also known that undegraded cereal starches after gelatinization in water at a concentration of about 5 to 12 fviasse-% dimensionally stable 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.

after functional groups are introduced into them by a chemical derivatization process.

The main disadvantage of the mentioned types of starches is that their gels made with water as Carriers or additives in food and food preparations are not suitable if this is due to the influence of temperatures below freezing point and prolonged storage Exposed to room or refrigerator temperatures. Such gels and starch dispersions suffer irreversible transformations during freezing, and the strength lies after thawing as water-insoluble, sponge-like mass. 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 changes in such a way that the gel hardens and repels water. Thereby appearance and other sensory properties negatively affected. All of the changes mentioned can go through

■ In this way, heating cannot be reversed.

There are other disadvantages to native strengths. that their gel-like preparations very often have one have a typical, sticky consistency and a characteristic, species-specific taste.

Such products are not suitable for use in foods or food preparations where it is important that they retain their shape after painting and spraying. A An additional disadvantage of the products mentioned results from the fact that, after the gelation by heating no phase transformation can be achieved and thus the subsequent homogeneous incorporation more firmly or, dissolved ingredients, e.g. B- of salts, sugar, coloring agents, Preservatives, among other things, are largely difficult 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 aqueous medium, according to the task, no tendency to association, gel formation or Cloudiness. A production of thennoreversible gels in an aqueous medium is with the degradation products DE-OS 19 55 392 is not possible. The content of high molecular weight degradation products is pushed back by the procedure The products that can be produced by this known process therefore fundamentally differ due to their properties from those of the method according to the invention, may be mentioned e.g. 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 in such a way that such preparations are manufactured can be, which with water> whitening! Form thermoreversible, neutral-taste gels that are freeze-thaw-stable and have a consistency of pasty to cut-resistant can be varied

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 substances with an intense odor and taste.

The process according to the invention for the enzymatic production of Siärkehydrolysenptodukte 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. of the incipient increase in consistency, and the degradation increases as it increases 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 until all irreversibly swollen .starch grains have dissolved continued. The starch is degraded within 5 to 30 minutes.

By means of the measures according to the invention, the heterogeneous enzymatic hydrolysis is carried out in such a way that some of the starch polysaccharides. namely the part in solution, which is broken down by the enzyme much faster and more extensively than the other part of the starch polysaccharides, which is in the solid phase within the swollen grains. Due to these two different physical states of the substrate, the enzymatic breakdown leads to hydrolysis products desired Moieküigrößenverteiiung _j wherein it must be noted that def nature of this distribution is not subsequently compensated by a too long incubation time in the actual temperature optimum of the bacterial alpha-amylase, which is at high substrate concentrations between about 8O ⁰ C • and 87 ° C again. It is therefore crucial for the process according to the invention that this temperature range is passed quickly during heating for the purpose of enzyme inactivation.

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

π addition of deodorizing and / or decolorizing materials, in a manner known per se from the hydrolyzate ⁿ separated. This is either converted into a gel by cooling or into a dry product by removing water. The dehydration is preferably carried out by spray drying. Roller drying and freeze drying have also proven to be useful.

Among the tuber and root starches, potato starch is the preferred starting substrate for the starch hydrolysis products to be produced according to the invention, starch concentrations of 25 to 30% by mass having proven particularly favorable. In addition, those low-substituted starch derivatives. Different pretreated starches can also be used, the swelling temperature range of which has been changed in comparison to untreated starches by certain pretreatment measures, preferably by artificial aging using heat-moisture treatment or by modifying the viscosity behavior using calcium or other ions.

In the "starch hydrolysis products" prepared according to the invention additions such as B. Nutrients and additives, food. Bring in food preparations and enzymes. This is especially important when low 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 the solutions added before their further work-up.

μ 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 starch hydrolysis product made from potato starch, these complexes have ^{an absorption maximum at (odnormalities of 4 × 10 4} N in the wavelength range 530 to 550 nm, which shifts to smaller wavelengths when the iodine concentration increases.
The starch hydrolysis products produced according to the invention with DE values of i> to 8% are not hygroscopic and, after dissolving in water, depending on the concentration, give pasty to cut-resistant white-glossy gels when a certain concentration of preferably 15 to 40% by mass - Below about 15 to 18% by mass, pulpy consistencies develop.

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

pasty, 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% by 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 Form prepared in water, preferably in gel form, as a carrier or additive 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 and others.

One area of application is based on the low hygroscopicity and the good water solubility of the Starch hydrolysis products. They can be used advantageously as drying aids and carrier substances Use dehydration of sensitive substances. z. B. in the spray drying of spices, Instant drinks (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-lending and water-binding additives to puddles. Cream dishes. Soups. Sauces. Coffee whiteners, ice cream mixes. Fruit drinks, vegetable concentrates. Milk drinks. Canned and prepared meals. To be highlighted Advantages in this area of application are the freeze-thaw reversibility of the gels, which is what the Production of frozen food is important, as is their ability to do so because of their meltability are miscible with aqueous liquids in any ratio. This is i.a. when applying the Starch hydrolysis products as an essential ingredient in sauces in canned fish, meat, vegetables and fruit in which the tissue water escaping from the sauce during sterilization without Phase separation must be included.

Additional areas of use for the starch hydrolysis products produced according to the invention result from the fact that their aqueous preparations are miscible with proteins, in that concentrated protein solutions such as egg yolk and egg white can be incorporated into the gels by mixing or by adding aqueous protein solutions ₍ e.g. milk, dry preparations) to the gels. Ie of the starch hydrolysis products prepared according to the invention can be dissolved and the mixtures can be brought to gel formation.

In many of the areas of application mentioned, it is of great application-technical 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 prickly peas the gels according to the invention such that none

lu further additives are required to produce haze and gloss. Because of this particular Properties, the gels according to the invention can be used as fat substitutes wherever the fat acts as a consistency builder in the conventional way: in cake creams and fillings, toppings, Mayonnaise and tartar sauce, cheese creams and other 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 T to be set. ckensubstanzhaltes be adapted to the desired application target 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 options 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 one

Sj is an easily digestible carbohydrate, the calorie content of which is only about half that of fat.

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

example 1

270 g of potato starch are placed in a 1 l three-necked flask (18.5% moisture) in 630 m! Suspended 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 of 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 corresponds to a concentration of 0.172 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) heated in two stages:

"a) Heating the system at a heating rate from 0.9 degrees Celsius per minute (heating level 1) to 6 ^ to 64 ° C:

b) further heating the system at a rate of about 4 degrees Celsius

^h "per minute (heating level 3) from 64" C to 100 C and maintaining this temperature for 15 min to completely inactivate the enzyme and to coagulate the proteins,

In this Pro'gfamm the Reaktionszeil is the degradation in the heterogeneous phase (temperature range 59-70 ⁰ C) NIID 8.2. The temperature range from 70 to 90 ^° C. (homogeneous phase) is traversed in 12 minutes.

The hydrolyzate obtained is then centrifuged to separate the protein, concentrated by evaporation in vacuo to a dry matter content of about 50% by mass, poured into trays, dried in a climate chamber with air circulation for 24 to 48 at 5O ⁰ C dried, ground and sifted. The starch hydrolysis product has a residual moisture content of 8.2% and a DE value of 5.2%.

in

Example 2

In a 20 l hanging vessel made of glass, 5.68 kg of potato starch (12.0% moisture) are suspended in 10.981 water and the pH is adjusted to 7 (dry matter content of the suspension = 30% by mass). After adding 9.28 ml of protein-free bacterial alpha-amyase, corresponding to a concentration of 0.125 I ^ MR / cr · - ·· —- · --.. -—--— ..— .--. ■ ·· .. -

Suspension with stirring (stirrer with a 120 mm blade, 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) hold this temperature for 10 minutes;

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

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

In this program, the reaction time during the degradation in the heterogeneous phase (temperature range 59 to 70 ^° C.) is 28.4 minutes. The temperature range from 70 to 90 ^° C. (homogeneous phase) is traversed in 15 minutes. The volume of the batch increases from the original 14.6 liters to 18.3 liters, and the dry substance content falls accordingly to 28.2% by mass. The hydrolyzate is filtered hot through a Dederon-Nessel filter cloth, concentrated in vacuo to a dry mass of 45% by mass and on an experimental drum dryer (drum heating 220 V, 33 kW, 3 heating levels) at a drum temperature of 115 to 125 ° C with a Feed rate of 30 ml / min dried. The starch hydrolysis product has a residual moisture content of 8.2%, a crude protein content of 0.1% and a DP value of R _- I% nnf

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 for two different iodine normalities for the wavelength of the absorption maximum (A _miI in rim) and the maximum extinction coefficient (e _m «), 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

50 by 1 cm:

15th

20th

Starch hydrolysis product
according to

DE

Measurement at iodine malality 4 10 ¹ N

t max ι max

[nm] Measurement of iodine normality 4 · 10 ⁴ N

example 1
Example 2

5.2
8.1

527 503 0.112
0.095

/ Max
[nm |

546
532

f max

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 by means of 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 (cf. Table) the system is under a heating rate of 15 degrees Celsius per minute Introduction of holding stages heated according to the following program, the consistency depending on the Time is registered:

a) heating to 59 ° C;

b) constant temperature for 15 min;

c) heating to 635 ° C;

d) constant temperature for 5 min;

e) heating to 65 ° C;

f) constant temperature for 5 min:

g) Heating up to 68 ° C:

hj 'constant temperature for 5 min;
i] 'heating to 90 ⁰ C ;.

In this program, the reaction time is min during the degradation in the heterogeneous phase (temperature range 59-70 ° C) 373rd 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. In the table are the at Using three different amounts of enzyme achieved maximum consistency and the appearance of the Sols indicated that by heating the respective gel is obtained at 80 ° C.

Amount of enzyme in viscograph units at the holding stages

[ml] 63.5 C 65.0 C

68.0 (

Appearance
of the sol
at SO C

0.25
0.22
0.20

50
210
100

100 150 490 ΙΟυ
240
26 ". ι

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

From the starch hydrolysis products prepared in Example 2, gels with different dry matter content are prepared by converting the appropriate amount of the dry product into a clear solution with a weighed amount of water while stirring and heating in a water bath to 80 ° C. To determine the gel strength, 70 ml of the solutions are poured into a Ridgelirrteterbecher smeared with silicone fat and stored at 4 ° C for 24 hours Penetration depth measured in mm (maximum penetration depth 20 mm).

To determine the melting behavior, ί 10 ml of the solutions with different flock substance contents are poured into test tubes and the gel is formed in the refrigerator within 24 hours. The glasses are individually placed in a spacious ^{water bath heated to 80 °} C. and the gel is brought to melt with a thermometer while stirring, the change in consistency being 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 content

Consistency characteristic

13.8
18.4
23.0
27.5
32.1
36.7
41.3
45.9

pulpy

the same

pasty

the same

the same

cut

the same

the same

Penetration depth of the Melting point Clear Standard body Point [mm] [Cl m 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

Example 5

In 75 ml of water, 25 g of the starch hydrolysis product prepared according to Example 1, 03 g table salt, 0.015 g sodium benzoate and 0.085 g of benzoic acid dissolved and, after cooling, 1 g of diacetyl-containing butter flavoring was added. As soon as the gel has formed in the refrigerator, 66 g margarine or butter or a Mix in these two fats. This mass has the consistency of natural spreadable fats Room or refrigerator temperature can be spread in the same way and gives that which is bound in the gel Water (about 53% by mass) does not come off 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 C different spices (vanillin, nutmeg, cinnamon, clove, cardamom, etc.) added thereto, and after cooling to about 40 ⁰ C with a at 80 ° 27 g of the Stärkehydrolysenproduktes prepared according to Example 2 together with 50 g of sugar dissolved, Cocoa paste, consisting of 25 g de-oiled cocoa powder, 5 g butter and 60 ml milk mixed with a whisk.If you stand in the refrigerator overnight, a mushy, flowing mass forms that can be used as a dessert, confectionery filling, cream for baked goods or as a spread . The fat content of this chocolate mass is approx. 4% by mass, it contains approx. 209 kcal / 100 g.

Example 7

In a homogenizer, 24.8 g of sunflower oil, 15.1 g egg powder, 4.7 g spice vinegar, 3.0 g sugar, 3.0 g mustard, 2.25 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 ToIIenser) with a fat content of 25.2% and a Proteinghalt of 29.5% are heated together with 10 ml of water and 0.5 g of salt melting at 85 ° C and cooled after complete melting at 50 ⁰ C At this temperature will be without

further heating 35.5 g of a gel, consisting of 25 g of starch hydrolysis product (prepared according to Example i), 0.025 g of an emulsifier and 75 g of water are stirred in and the initially mushy, flowable mass into one Put in the refrigerator After 48 hours, the mass is spreadable. It contains 8.9% fat and 173 kcal / 100 g.

Claims (3)

Patent claims: 1. Process for the enzymic production of starch hydrolysis products from starch, soft 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 min takes place with continuous or gradual rise in temperature, after adding the bacterial alpha-amylase is first heated to a temperature 1 to 4 degrees Celsius below the Range of the swelling temperature of the starch used in each case, followed by heating up to to the upper limit of the cooling 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.