NL1005246C1 - Means against starch retrogradation. - Google Patents

Description

MIDDLE TBOBN STARCH RETROGRADATXE

The present invention relates to an agent for inhibiting or inhibiting the retrogradation of starch.

Starch is the main nutrient reservoir in plants. As a result, starch practically always occurs in vegetable foods for humans and animals, and then not only in direct vegetable products such as vegetables and the like, but also in derived foods based on, for example, flour or flour, such as bread and pasta products.

Starch consists of two components, amylose and amylopectin. The unbranched amylose consists of glucose molecules, which are linked to each other by means of an α-1,4 bond. Amylopectin is branched and has about one α-1.6 bond per thirty α-1.4 bonds.

Starch has been found to retrogradate over time. Retrogradation means that dissolved starch transitions from an amorphous state to an insoluble, aggregated, crystalline state. The retrogradation mainly occurs in the amylose molecules. However, amylopectin also retrogrades in the long term, which is likely caused by the outer chains of the amylopectin. The retrogradation of amylopectin occurs, for example, in the "aging" of bread and pasta.

Retrogradation of a starch solution or starch paste produces a number of physical effects. For example, a starch paste thickens and becomes viscous during aging. Furthermore, turbidity and tendency to form solid gels arise. A "sheet" is formed on a hot paste. In addition, insoluble aggregates are formed that can precipitate and syneresis (a process in which expulsion of the continuous phase by shrinking of a network) of water in pasta occurs. Retro-35 gradation includes processes such as phase separation, crystallization and gel formation.

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There are known means of counteracting retrogradation of starch, such as, for example, enzymes (eg x-amylase), proteins, sugars (eg Dimodan ™, SDS. However, some such inhibitors are not suitable for use in foodstuffs.

It is the object of the invention to provide an alternative means that counteracts or inhibits starch retrogradation and which can moreover be used in foodstuffs.

Surprisingly, this aim has been found to be attainable after observing the phenomenon that sterilized peas in pots often form a haze and / or white precipitate, while that in peas with carrots is rarely observed. Further research according to the invention led to the determination that the haze and / or the white precipitate is formed by retrograded and flocculated starch. It was also shown that in the pots with peas in combination with carrots, no cloudiness and / or precipitation occurs due to retrogradation. This is despite the fact that, in combination with carrots, more starch is in the liquid phase. It was deduced from this that carrots excrete one or more components that prevent retrogradation.

The same observation was made with the infusion of green beans. This infusion was also able to inhibit starch retrogradation.

Further investigation has shown that the constituents of the infusion responsible for its retrogradation-inhibiting effect are in any case uronic acids. A particularly suitable uronic acid is galacturonic acid, a product formed in the heat degradation of pectins. Other uronic acids are, for example, glucuronic acid, mannuronic acid, xyluronic acid, iduronic acid, etc.

According to the invention there is therefore provided a means for counteracting or inhibiting the retrogradation of starch, comprising an extract of processed vegetables, in particular carrots and / or green beans and / or one or more components thereof.

Retrogradation of starch can be a problem in many areas. The retrogradation inhibitor according to the invention can be used in all these areas where starch is used. An important example is the use in bread and pasta products. The agent according to the invention then prevents the aging of bread and pasta. In addition, the agent can also be used for non-food applications of starch, such as coatings and the like.

The aforementioned problem of the white deposit in pots of peas can now also be prevented by adding the agent according to the invention to the infusion (the moisture in a jar (sterilized) product) of the peas.

The agent according to the invention in its most basic form simply comprises an extract of carrots. In addition, one or more components from this extract can also achieve the desired effect. As already mentioned, such components are, for example, galactonic acid or oligomers thereof. Alternatively, other uronic acids such as glucuronic acid, mannuronic acid, xyluronic acid, iduronic acid, etc., or oligomers thereof or positively charged polymers (such as polylysine) can also be used for the same effect. These acids can be isolated from the infusion, but are also available as such. Alternatively, positively charged polymers (such as polylysine) can also be used for the same effect. Such components may then also be found in other sources.

In addition to the agent itself, the invention further relates to use of the agent in the aforementioned applications, as well as to a method for counteracting the retrogradation of starch in starch-containing foods, comprising adding a retrogradation inhibitor of the invention.

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The invention will be further illustrated in the following examples. However, the examples are given for that purpose only and are not intended to limit the invention in any way.

5 EXAMPLES EXAMPLE 1

Starch retrograde in pots of peas

The research that led to the present invention was started with the hypothesis that the turbidity in jars of canned peas is caused by retrograded starch. To investigate whether this hypothesis was correct, the infusion of clouded pots was analyzed.

For this, peas were sorted into two sorts (sort I <7.5 mm and sort II 7.5 - 8.2 mm) and blanched for 2 minutes (sort I) or 3 minutes (sort II) in water of 90 ° C. Then they were cooled under cold running water for 5 minutes and drained for 5 minutes. 370 ml jars were then filled with (235 ± 1) g peas. To this was added 100 ml of infusion (1% salt) and the peas were sterilized at 118 ° C with 1.8 bar pressure for 35 min. In the pots, over time, a white precipitate formed. The 25 sterilized peas, the infusion and the sediment were analyzed after 25 weeks to assess the composition of the sediment. Table shows the results of the analysis.

Starch content of sediment (g / 100 g freeze-dried); protein content of infusion (mg / 100 g); amount of sediment (mg freeze-dried / pot) (sample codes: grading I and II) 1005246 5

Sample Starch,% Protein Amount of peas sediment infusion sediment raw 25wk 25wk 25wk 25wk 5 _ AI 1.6 1.0 99 ± 2 407 103 A II 2.0 1.3 98 ± 10 549 436 BI 5.2 3.5 99 ± 8 361 59 10 B II 6.9 5.8 98 ± 8 511 69

Over time, it was found that more than 30% of the starch from the peas diffuses in the infusion: after 25 weeks, sediment is formed, which is 100% starch, while the protein remains in solution. It follows that turbidity in the pots of peas is due to the retrogradation of starch.

20 EXAMPLE 2

Prevent white precipitation from carrots

Based on observations, it was believed that the infusion in pots peas and carrots prevents formation of the white precipitate normally formed in peas only. This example was performed to confirm this assumption.

Too ripe peas, both round and wrinkly, of grades 2 or higher (diameter 30> 7.5 mm) were used. The infusion of too ripe peas quickly becomes cloudy. The peas were blanched in 90 ° C water for 3 minutes. They were then cooled under cold running water for 5 minutes and drained for 5 minutes.

Carrot was used as a carrot with a diameter of 10 to 20 mm and a length of 50 nun. The carrot was placed at 10 atm for 30 seconds. and steamed at 180 ° C.

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The weight ratio in the packaging unit was: infusion (water with 1% NaCl): pea: carrot - 58: 43: 43. The whole was sterilized in a 370 ml glass jar for 30 minutes at 118 ° C with a heating time of 10 minutes. .

In addition, an aqueous wax carrot extract was used as root infusion. This aqueous extract was prepared by washing carrots, breaking them and then steam peeling. Large pieces were cut. 370 ml jars were filled with 240 g of carrots. To this was added 100 ml of pour-on (1% saline). Then sterilized at 118 ° C for 35 minutes. The resulting infusion was clear and did not need to be centrifuged.

The relative turbidity of the pots was determined spectrophotometrically at 780 nm. The cloudiness of the peas alone was set at 100%. Figure 1 shows the result of 4 experiments with pots of peas in comparison to pots of carrots and peas. This shows that the addition of carrots significantly reduces the turbidity.

Figure 2 shows a comparison of pots of peas, pots of peas and carrots (P) and pots of 25 peas with a rooting infusion (WP). This shows that the carrot extract has an even greater effect on the turbidity than the carrots themselves.

EXAMPLE 3 Soectrometric Determination

The starch retrogradation can be monitored by spectrophotometric measurements at 780 nm. This is used in this experiment.

To make a test solution of starch flour, a suspension was made of about 1% starch (so-called "soluble starch" or corn starch) in the medium to be tested (water or root infusion) in a test tube. In some cases, a retrogradation inhibitor (10% SDS

1005246 7 or Dimodan ™ based on the amount of starch) added. The suspension was heated in a boiling water bath for 15 minutes with continuous mixing to prevent the formation of a lump at the bottom of the tube. After heating, the solution was cooled to room temperature. After this, if they were already cloudy or if not all of the material had been solubilized, the samples were centrifuged in a pellet at 12,000 rpm for 15 minutes. The supernatant was then placed in a cuvette and the retrogradation was monitored therein using a spectrophotometer at 780 nm or by eye, since cloudiness was often very evident. The table below shows the composition of the test solutions used.

15 _

^ SI ^^ SSS ^ 3S ^ S! ^^ S ^ S & SSEflB ^^ SI

Test Solution- Material Medium Inhibitor I

sing no .____ fl _1__ starch__water __-_ _2__ starch__water__SDS_ 20 _3__ starch__water__Dimodan ™ _ 4 starch root infusion

Figure 3 shows that the root infusion (Test 4) inhibits retrogradation compared to the blank (starch in demineralized water; Test 1). The effect of the infusion was lower than that of the known inhibitors SDS and Dimodan ™ (tests 2 and 3), but still acceptable.

EXAMPLE 4 Retroaration inhibitions by green bean varieties

The infusion of sterilized green beans has the same retrogradation-inhibiting properties as the infusion of carrots.

The green beans were infused by spearing, breaking and washing 35 beans. The beans were then blanched at 90 ° C for 4 minutes. After cooling and draining (± 5 minutes), 720 ml jars were filled with 410 g green beans. To this a 1% 1005246 8 salt solution was added until a headspace of ± 8 nn was created. The jars were now sterilized at 118 bar at 118 ° C for 30 minutes.

The same experiments as described in Example 3 for the root infusion were carried out with the infusion thus obtained. The results of the green bean infusion are also shown in figure 3.

▼ EXAMPLE 5 10 Carrot extract keeps starch in solution

To determine the degree to which starch (amylopectin, amylose or both) from the peas enters the infusion during the heating step, various starch and amylose assays have been performed. These experiments were aimed at investigating whether the effect of the root infusion is possibly based on preventing the diffusion of starch (amylose) to the infusion.

The starch determinations were made on peas heated without carrots, on the infusion of these peas, on peas heated in the presence of carrots and on the infusion of these peas. 50 g of pea samples were homogenized with 50 ml of water. The homogeneous mixture was used for the starch determination. The infusion was used directly.

As a control, the starch content of root infusion was also determined, after which a balance was drawn up for the total starch present. These tests were performed on two different grades of peas.

The starch determination was an adapted version of the Boehringer test kit for starch determination.

The results of the starch determinations in peas, pea infusion, peas in the presence of carrot and infusion in the presence of carrot are shown in Figure 4.

The starch content in carrot infusion appears to be negligibly small and therefore did not affect the results. Figure 4 shows that in the infusion in the presence of carrots more starch (amylose) goes into 100524 6 9 solution. In pots with only peas, with less starch in solution, retrogradation does occur more quickly. The same result was found for two different sorts of peas, only the total starch content in the pot differed. These results undermine the hypothesis that components from the root infusion form a kind of barrier that prevents diffusion of starch to the infusion. Apparently, the root extract or a component thereof has a direct effect against the retrogradation of starch.

EXAMPLE 6

Application of carrot extract in bread

This example was performed to study the effect of the carrot extract on bread aging.

To see the effect of the carrot extract in bread, a number of breads were baked. The breads were made from flour, water and yeast 20 (500: 300: 15). In order not to suffer from any retrogradation inhibition due to the presence of fats, no fat was added during baking. In the "carrot loaves" the water was replaced by root infusion. The breads were packed in plastic bags to prevent drying. Of the loaves, only the crumb was used for the experiments.

The crumb was ground using a food processor. From the crumb, FT-IR (Fourier transform infrared) spectra were measured on a BIO-RAD FTS-60 spectro-30 meter, with a resolution of 8 cm * 1 using an MCT detector. The IR spectra of the bread samples were measured by placing the sample on an attenuated total reflectance (ATR) attachment with a ZnSe crystal. Fourier self-deconvolution was applied to all spectra to improve the resolution.

The FT-IR / ATR method is known per se and is widely used. The technique of FT-IR spectroscopy in combination with attenuated total reflectance 100524e 10 (ATR) can be used to track the retrogradation of starches. During storage of this material, changes are expected in the spectral region of 1200-1000 cm -1, which are assigned to vibrations of 5 C-0 and C-C bonds.

Furthermore, starch determinations were made on the breads, as described above, and the dry matter content was monitored during the aging of the bread. About 2.5 g of the sample was weighed into an aluminum weighing tray to determine the dry matter content. This tray was placed in an oven at 70 ° C overnight. The tray was then placed in a 105 ° C oven for 3 hours. The tray was then weighed again. The dry matter content is the difference between the first and second measurements.

There was no difference in taste and texture between the loaves with and without carrot and no difference in color. However, the IR spectra (Figure 5) showed differences between the two types of bread. Bread A 20 is baked with water, bread B is baked with carrot on top. The differences in the spectra mainly existed in the formation of bands in the carrot bread at 1730 cm -1 and 1380 cm -1. The intensity of a number of peaks at 1000-1200 cm'1 also seems to be different. This is due to a number of changes caused by retrogradation of starch.

The starch content of the loaves was between 45 and 50% for the different loaves. This corresponds to literature values.

When the dry matter content of the breadcrumbs is monitored, a slight decrease can be seen in both breads, from about 65% to 60%. There was no difference in dry matter content between the two loaves.

EXAMPLE 7

Effect of carrot and green bean extracts on bread aging 1005246 11

To quantify the effect of carrot and green bean extracts on bread aging, the following experiment was performed.

Four different breads of different compositions were baked. The composition is shown in the table below. Bread A is a blank, bread B contains only carrot extract, bread C also contains fat, and bread D contains a green bean extract.

10 _

A B C D

flour 500 500 500 500 sugar + + + + 15 salt + fat 50 water 300 - - - carrot extract - 300 300 green beans - - - - 300 20 yeast extract 15 15 15 15

After baking, the breads were analyzed by measuring the FT-IR / ATR spectra of crumb. The spectra were recorded over time for 48 hours. Since the breads did not contain any antimicrobial agents, they could not be stored for more than 48 hours. An increase in absorbance at 1047 cm -1 was observed. The spectra 30 were unraveled and the ratio A ^ 7 / ^ 150 of the absorption intensity at 1047 cm -1 (which changed over time due to the starch retrogradation) and 1150 cm * 1 (which did not change) was calculated. The results are shown in the following table: 35 1005246 12

Time ^ 1047 / ^ 1150

[h] Bread A Bread B Bread C Bread D

5 0 0.86 0.89 0.90 0.92 2 0.85 0.94 0.78 0.87 4 0.89 0.97 0.88 0.93 6 0.92 0.96 0.85 0.87 23 1.01 0.97 0.87 0.88 10 47 1.12 0.98 0.87 0.94

Increase factor,%: 30.2 10.1% 0% 2.2% 15 r48 / r0: 1.31 1.10 1 1.02

The data show that in the case of bread containing only water, a 30% increase in the A1047 / A1150 ratio is observed, while for breads prepared with carrot or green bean extracts, the increase is 10.1% and 2, respectively. Is 2%. No increase in the A1047 / A1150 ratio was determined for bread C, which contained both carrot extract and fat. Since the increase in the A1047 / All50 ratio is linked to the retrogradation of starch, it can be said that the extracts of carrot and green beans had an inhibiting effect on the aging of bread, which is induced by starch retrogradation.

30 EXAMPLE 8

Retroaradat-emTnftwd effect of uronic acids

To a Pierce test tube with 1.5 ml of a 2% starch suspension and 0.1 M acetate buffer pH 5, 1.5 ml of a galacturonic acid solution was added, so that the final concentration of starch and uronic acid are 1% and 24 mM, respectively. The solution is mixed well 1005246 13 and then heated to 100 ° C with shaking in a Pierce block for 15 minutes. The solution is then cooled to room temperature by immersing the tube in a water bath for 5 minutes. After centrifugation at 12000 rpm (15 min.), The solution is transferred to a 1 ml spectrophotometric cuvette and incubated at 4 ° C for at least 1 week. The absorbance at 780 nm is monitored over time. The variation of the absorption of the solution is compared to that of a controller, prepared in the same manner, but with the difference that instead of the uronic acid solution, water was added to the starch suspension in the same ratio as the sample . In addition, a sample with 0.1% Dimodan as a retrograde 15 inhibitor was tested. Figure 6 shows that galacturonic acid in the concentration used inhibits starch retrogradation.

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Claims (6)

Means for inhibiting or inhibiting the retrogradation of starch, comprising an extract of processed vegetables, in particular carrots and / or green beans and / or one or more components thereof. Retrogradation inhibitor according to claim 1, characterized in that the component is selected from uronic acids, such as galacturonic acid, mannuronic acid, glucuronic acid, xyluronic acid, iduronic acid or positively charged polymers, such as polylysine. 3. Retrogradation inhibitor according to claim 1 for use as a bread improver. Retrogradation inhibitor according to claim 1 for use in pasta products. 5. A method for counteracting the retrogradation of starch in starch-containing foods, comprising adding a retrogradation inhibitor according to claim 1. 6. Use of uronic acids, such as galacturonic acid, mannuronic acid, glucuronic acid, xyluronic acid, iduronic acid or positively charged polymers, such as polylysine, to inhibit or inhibit starch retrogradation. 1005246