BR102016030414A2 - process of obtaining mixed resistant type 3 and 5 starch, obtained resistant starch and use - Google Patents

Description

(54) Title: PROCESS OF OBTAINING TYPE 3 AND 5 MIXED RESISTANT STARCH, RESISTANT STARCH OBTAINED AND USE (51) Int. Cl .: A23L 7/17; A23L 29/00; C08B 30/00; A23L 29/212; A23P 10/47 (73) Holder (s): UNIVERSIDADE ESTADUAL DE CAMPINAS - UNICAMP (72) Inventor (s): MÁRCIO SCHMIELE; LUCAS KOUJI TOKUUE HORI; MARIA TERESA PEDROSA SILVA CLERICI; YOON KIL CHANG; MÁRCIO SCHMIELE; LUCAS KOUJI TOKUUE HORI; MARIA TERESA PEDROSA SILVA CLERICI; YOON KIL CHANG (74) Attorney (s): FERNANDA LAVRAS COSTALLAT SILVADO

3.2S

2 M

Afttaôode corn ertruMdo

I

1/35

PROCESS OF OBTAINING TYPE 3 AND 5 MIXED RESISTANT STARCH, RESISTANT STARCH OBTAINED AND USE

Field of the invention:

[001] The invention described here falls within the field of food engineering, and makes reference to a process for obtaining mixed resistant starch of type 3 and 5 pregelatinized by thermoplastic extrusion.

Fundamentals of the invention:

[002] Starch is an important carbohydrate for the human diet, but to be an energy source, it must go through the gelatinization process and when consumed by man, it will be hydrolyzed by maltose, maltotriose and dextrin amylases, which will again be hydrolyzed by amyloglucoxidases monosaccharide (glucose), which is absorbed. The glucose provided by the starch is a source of energy and its excess will be stored as fat.

[003] In the last decades, food has been characterized by an increase in the consumption of fats and carbohydrates that are easy to digest, resulting in the rapid supply of energy to the body, which has reflected in the increase in weight of the population, favoring several diseases such as obesity, hypertension and heart disease.

[004] It is not yet clear the relationship between dietary fiber and obesity, however a diet with adequate amount of dietary fiber can give satiety from foods with less energy. Diets with low fiber content have more energy and can promote obesity and increase the risk of diabetes, as soluble and viscous fibers can delay the absorption of

2/35 sugar from the small intestine, minimizing blood glucose spikes.

[005] Technologically, foods containing high levels of dietary fiber have a strong taste and odor and some are not palatable, having a thick texture and unpleasant mouth feeling. Therefore, resistant starches emerge as one of the ingredients that can yield high quality products, even presenting better sensory qualities than products containing fibers.

[006] Resistant starches have nutritional characteristics typical of dietary fibers, acting like other non-starch polysaccharides, and serving as a source of carbohydrates for the large intestine and colon microbiota. Another physiological effect observed is the prolongation of the feeling of satiety after eating starchy foods with a low glycemic index and control of blood lipids.

[007] Resistant starch, from now on, called AR, can be defined as the sum of starches or their respective degradation products that resist enzymatic digestion in the small intestine. Of the five types of RA, two types are modified by physical processes and after modification are used as ingredients. These important types for Food Engineering are type 3 resistant starch (AR3) and type 5 resistant starch (AR5).

[008] AR type 3 (AR3) is a retrograded starch that can be obtained with cooking and cooling cycles, to promote the retrogradation of amylose. The retrograded starch

3/35 has the advantages of not being dissociated in conventional cooking processes, as it requires temperatures above 170 ° C to break the recrystallized area (AR3). The starch's retrograded area will not be hydrolyzed by the enzymes, due to changes in the active site, which does not bind to amylase. This type is considered stable to thermal treatments, having cold viscosity and solubility in water.

[009] Production using the cooking method is the most studied and used for the production of AR3. This heat treatment is carried out in an autoclave at high temperatures and for a long time, varying the cooling time and cooking and cooling cycles. Because it is previously gelatinized, AR3 has cold viscosity, high solubility and water absorption, and can be used directly as a thickener or stabilizer. The disadvantages are the very high cost, due to the long heating and cooling cycles, and the starch production takes over five days and after the process, it has to undergo drying, since they were treated as starch pastes in proportions above 1: 3 (starch: water).

[0010] Up to the present moment, the state of the art presents tests carried out in the starch process by thermoplastic extrusion to produce resistant starches that are not successful, with values below 5% being obtained.

[0011] The type 5 AR is formed when the starch complexes with lipids, forming complexes with the amylose fraction. The compounds used are derived from fatty acids and alcohols. When forming a complex helical structure with amylose, it does not have the active site available for enzymes

4/35 amylolytic. This type of starch is in granular form and is considered stable to heat treatments.

[0012] The use of thermoplastic extrusion processes to produce gelatinized starch is based on the fact that it is a versatile, fast process and that with minor modifications in the process, such as moisture of the raw material, extrusion temperature and degree of shear, can - different starchy ingredients are obtained, as it can be gelatinized.

[0013] The document CN103621870 refers to a process for obtaining AR-5 and analyzing the process, the following disadvantages are observed: the best results are obtained only with high amylose starch; the long reaction time, which can last up to 4 days, which is in several stages, with various temperature gradients (60 to 120 ° C); makes use of various equipment with temperature control, but it is not a continuous process; the method leads to almost frying the starch in oil; the use of triglycerides, in the form of oil or fat (triacylglycerols), can lead to product rancification in two forms: oxidative and hydrolytic; the presence of the use of organic solvent (ethanol) to disperse the suspension of starch and fat at the beginning of the process, leading to the need for its subsequent evaporation; the formed starch may have a high caloric value, due to the added fat content (5 to 25%), in addition to being a starch that may have excess lipids, which has not been complexed and will be digested by the digestive system; technologically it can interfere in food applications, the fat of which can harm the final product, as examples in juices; can develop

5/35 odors during storage; and finally, it may have low storage stability.

[0014] The technology developed differs from the technology presented in the mentioned document since fatty acids were selected that will not undergo the oxidative rancification process and there will also be no hydrolytic rancidity as they are saturated free fatty acids. The fatty acids will have a more efficient performance in the complexation with the amylose chain, due to being in the free form, and not in the esterified form as triglyceride (oil or fat). In addition, a one-step process will be carried out, with humidity variations of 15 to 25% (m / m) and temperature of up to 170 ° C. During the extrusion process, the fatty acid will complex with the starch, with no excess of uncomplexed fat. Still, there was no need to use organic solvent. Fatty acids will be complexed with starch, which will be partially resistant to digestion, not increasing the caloric value of the product. The formed product can be consumed as snacks directly, in the preparation of instant powders or used as pre-gelatinized starch with a high degree of resistance.

[0015] The document US20110256261 describes a process using granular starch preferably with a high amylose content that will be heated between 60-121 ° C. This process presents as technical problems the fact that the optimization of the process goes through several stages, the highest yields are with starches with a high amylose content, and the heat treatment time is long. In addition, the starch obtained

6/35 must undergo another heat treatment to be consumed, as it is in granular form.

[0016] In the developed technology, the starch loses its granular form, as it is gelatinized and complexed at the same time, therefore, what is resistant will resist heat treatments when used in food. In other words, a versatile process was developed, where you can have the product ready for consumption or transform this product into a pre-gelatinized starch type ingredient with high resistance to enzymatic digestion. This starch already has cooling viscosity.

cold and low retrogradation during [0017] The document MX2012003871 describes a method of preparing resistant starch in a single extrusion step in which resistant type 4 starch was produced, considered chemically modified AR, using high temperatures and high concentrations of chemical reagents . The starch obtained is limited in the concentrations used for the preparation of products, its consumption is limited to the content of chemical reagent allowed for consumption. The chemical reagents are all based on phosphate hydroxyl groups,

being that the excess free in phosphor that didn't react was removed from the product. At traditional modification with phosphating, the excess in reagent phosphated must to be withdrawn, to avoid damage to body human and interactions with food. [0018] A technology developed differs by having in

since in the presented process there was the formation of starch with resistance to enzymatic digestion, which can act as dietary fiber, being considered an ingredient and without

7/35 usage limits, as it is safe for consumption. The resistant starch in question was obtained through the thermoplastic extrusion process, using native starches, fatty acids and different conditioning humidity of the raw materials, submitted to heat treatment (80 to 170 ° C) in a thermoplastic extruder. In addition, the resistant starch obtained in the developed process is a mixed type 3 (retrograded) and type 5 (complexed with lipids), and can be consumed without concentration restrictions. This starch does not undergo chemical modification, only the fatty acid is physically involved within the amylose molecules of the starch. The starch must be considered mixed, since only the thermoplastic extrusion provides the formation of a resistant starch of type 3, a retrograded starch, which no longer has the original granular structure of the starch, which presents resistance to enzymatic digestion, however as already mentioned, in very low concentrations, being considered a pre-cooked starch. Together, in the formation of AR5, the processes keep the starch in granular form and the use of fatty acids that will bind to the amylose portion, so much so that this type of starch is obtained preferably with starches with a high content of amylose and not it is considered pre-cooked.

[0019] In the present invention, the starch loses its granular structure and at the same time becomes entangled with fatty acids, so it can be considered a mixed starch containing portions of AR3 (retrograded) and AR5 (amylose molecules, oligosaccharides and others folded with fatty acids). One of the advantages of use is the possibility of obtaining AR with any type of starch and the resulting AR

8/35 will be pre-cooked and or instant, that is, ready for consumption. 0 Physicochemical changes and resistant-starch content of extruded cornstarch with and without storage at refrigerator temperatures, by NEDERSUAREZ, David et al, describes an extrusion process used to produce resistant starch type 3 (retrograded), but sees the effect of variations moisture, extrusion temperature and screw speed, showing that the process produces resistant starch below 1.1 g / 100 g, since this process dextrinizes and / or gelatinizes the starch making it not very resistant and quickly digestible.

[0020] The technology developed is a process for obtaining mixed resistant starch types 3 and 5, with the use of appropriate fatty acids and the extrusion process.

[0021] The document Preparation and properties of resistant starch from corn starch with enzymes, by GAO, Qunyu et al. (2011), describes the use of enzymes to debranch the starch and then autoclaving to increase the concentration of type III resistant starch. Four steps are performed: 1) in a starch paste with 6% (w / w), use of alpha-amylase and high temperature treatment at 140 ° C / 20 minutes in an autoclave; 2) the gel formed is cooled and a second enzyme, pullulanase is used, and the enzyme starch suspension is maintained at 45 ° C / 24 hours; 3) the starch is cooled and kept at 4 ° C / 24 hours, and 4) the starch is dried and ground. The whole process takes 3 or more days and the maximum resistant starch content was 19% (w / w).

[0022] The technology developed concerns a fast process (a few minutes), since the thermoplastic extrusion process can be '’considered a

9/35 HTST processing - high temperature short time, that is, high temperature in a short period of time. In addition, it does not use enzymes or processes with high humidity, such as suspension of starches, nor cooling for 24 hours. The extrusion process comprises only one step and the obtained starch is ready for consumption or can be milled for use as an ingredient.

[0023] Thus, the present invention relates to a process for obtaining mixed resistant starch of type 3 and type 5 pre-gelatinized by thermoplastic extrusion.

Brief description of the invasion:

[0024] The present invention relates to a process for obtaining mixed resistant starch of type 3 and type 5 pregelatinized which comprises the steps of mixing and homogenizing at least one fatty acid to the starch; means for adjusting the moisture of the resulting mixture in the previous step; extrude in a thermoplastic extruder with gradual heating from the feed end to the end of the die; and obtaining the mixed resistant starch type 3 and 5 pre-gelatinized. In addition, the process comprises optional drying steps; cover or dredging; moisture adjustment and grinding to powder granulometry.

[0025] The invention also describes the resistant starch obtained and the uses of the products obtained by the process.

Brief description of the figures:

[0026] To obtain a total and complete visualization of the object of this invention, the figures to which reference is made are presented, as follows.

10/35 [0027] Figure 1: shows the expansion index behavior for each type of starch: corn starch (Figure la), cassava starch (Figure lb), sorghum starch (Figure lc) and starch with high content of amylose (Himaize type) (Figure 1d), using starch without (lower content of resistant starch) and with fatty acids (higher content of resistant starch).

[0028] Figure 2: presents the contents of resistant starch and digestible starch for extruded corn starch with and without the presence of fatty acids.

[0029] Figure 3: presents the data for the instrumental color and it appears that the tones are very similar, due to the very close values for the parameters L, a * and b *, indicating that there was no considerable color change that could alter the color of the starch to be used as an ingredient.

[0030] Figure 4: shows the values of water solubility index (a) and water absorption index (b) for extruded corn starch without and with the addition of fatty acids.

[0031] Figure 5: shows the viscoamylographic curves of the samples, being (a) referring to extruded corn starch without the presence of fatty acids and (b) with the presence of fatty acids.

[0032] Figure 6: shows the contents of resistant and digestible starch in the samples, observing a significant increase in the content of resistant starch with the use of fatty acids.

[0033] Figure 7: presents the data for the instrumental color of the extruded cassava starch.

11/35 [0034] Figure 8: shows the values of water solubility index and water absorption index, being (a) water solubility index and (b) absorption index

of water, for extruded cassava starch without and with addition of acids fatty. [0035] Figure 9: features the behavior

viscoamylographic for extruded cassava starch without (a) and with the presence of fatty acids (b).

[0036] Figure 10: shows infrared spectra for extruded cassava starch without (a) and with the presence

fatty acids (b). [0037] Figure 11: presents the contents in starch resistant ; and digestible starch for the starch in sorghum extruded with and without the presence of fatty acids • [0038] Figure 12: shows the color instrumental to starch from extruded sorghum with and without presence From acids

fatty.

[0039] Figure 13: shows the water solubility index (a) and water absorption index (b) for extruded sorghum starch with and without the presence of fatty acids.

[0040] Figure 14: shows the viscoamylographic behavior for extruded sorghum starch without (a) and with the presence of fatty acids (b).

[0041] Figure 15: shows the spectra for extruded sorghum starch without (a) and with the presence of fatty acids (b).

[0042] Figure 16: shows the contents of resistant starch and digestible starch for Himaize corn starch extruded with and without the presence of fatty acids.

12/35 [0043] Figure 17: shows instrumental color for Himaize corn starch extruded with and without the presence of fatty acids.

[0044] Figure 18: shows the water solubility index (a) and water absorption index (b) for Himaize starch extruded with and without the presence of fatty acids.

[0045] Figure 19: shows the viscoamylographic behavior for Himaize corn starch extruded without (a) and with the presence of fatty acids (b).

[0046] Figure 20: shows the infrared spectra for Himaize corn starch extruded without (a) and with the presence of fatty acids (b).

Detailed description of. invention:

[0047] The present invention relates to a process for obtaining mixed resistant starch of type 3 and type 5 pregelatinized which comprises the following steps:

a) Mix and homogenize at least one fatty acid to starch, preferably the mixture of palmitic acid with stearic acid in a ratio of 4: 6, respectively, in concentration of one to ten percent, preferably five percent, considering each fatty acid isolated or the sum between the combinations;

b) Means for adjusting the humidity of the resulting mixture in step (a) until a humidity range of 14 to 25% (w / w) is obtained, preferably 20% (w / w);

c) Extrude in a thermoplastic extruder at temperatures between 80 and 170 ° C with gradual heating from the feed end (input of raw material) to the end of the

13/35 matrix (product output), and minimum screw rotation speed of 80 rpm;

d) Obtain the resistant starch mixed type 3 and 5 pre- gelatinized. [0048] On step (a), the starch is selected of group that understands cereals, roots, tubers or stems, preferably starch from corn, which may be normal,

waxy or high in amylose. The fatty acid is selected from the group comprising lauric, myristic, palmitic and stearic.

[0049] In step (b) the means for adjusting the humidity comprise adding water, adding water vapor, or drying or any other means that allows to reach the humidity of 14 to 25% (m / m).

[0050] The advantages of obtaining a starch processed by extrusion are in the speed of the process and in the efficient control of the dependent variables such as expansion, desired degree of viscosity, water absorption and water solubility content and, mainly, the content of resistant starch, obtaining both the product ready for consumption and instant powder for use as an ingredient.

[0051] The product obtained in (d) may optionally be subjected to drying to humidity below 6% (m / m), if it is intended for direct consumption as breakfast cereal or snacks, and may also be subjected to coverage or dredging to fix aromas and flavors.

[0052] Optionally, adjust the humidity until the product obtained in step (d) has a humidity of less than 15% (m / m), grind to powder granulometry, to allow the use of this as an ingredient in the preparation

14/35 can be applied to obtain thickening or water retention without the use of heat, such as puddings, soups, broths, instant dairy mixes and breakfast foods; to prepare ready-made bread mixes; for use as a binder in the meat industry; or for filling fruit tarts, as they do not require the use of heat and increase aroma retention.

Examples of implementation:

Example 1 [0053] Obtaining breakfast cereal or expanded extruded with the addition of 3.62% palmitic acid, 4.79% stearic acid and 20.26% moisture of the raw material. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, flow rate of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final humidity below 6% (m / m).

[0054] Corn, cassava, sorghum and high amylose starch (Himaize type) starches were tested. Figure 1 shows the behavior of the expansion index

for each one From types in starches: starch of corn (Figure 1.a), starch in manioc (Figure l.b), starch from sorghum (Figure l.c) and starch with high content amylose (type

Himaize) (Figure l.d). It can be seen in this figure that the starches containing the fatty acids showed less expansion, due to the effect of this on the extrudate, which does not prevent its use as a breakfast cereal product and in the case of sorghum starch, this low level of expansion is directly linked to fiber rich products, all type

15/35 bran. The breakfast cereal produced with cassava starch in the thermoplastic extrusion process when compared to a control without fatty acid, showed a color similar to the product used as a control, with only a decrease in expansion.

[0055] The breakfast cereal produced with sorghum starch in the thermoplastic extrusion process when compared to a control without fatty acid, presented a color similar to the product used as a control, with only a decrease in expansion, but remaining within the expected for breakfast cereal and snacks.

Example 2 [0056] Extrusion of corn starch added with 2.5% palmitic acid and conditioned to 19% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed rate of 8 kg / h and matrix with 30 mm ² opening . Then the product went through a drying process until final humidity below 15% (w / w), followed by crushing to a particle size below 250 pm.

[0057] Resistant and digestible starch tests were carried out, according to the AACCI (American Association of Cereals Chemits International), color measurement in the cieLab system, water solubility and absorption tests and paste viscosity, in equipment called Rapid Visco Analyzer .

[0058] The contents of resistant starch and digestible starch were determined as described in method 3240.01 of AACCI (2010), where the digestible starch and resistant starch are determined. The sample was subjected to

16/35 an in vitro digestive process, with several amylolytic enzymes and the non-digestible fraction was quantified as RA. According to Goni et al (Goni, I. Garcia-Diaz, L. Manas, E. Saura-Calixto, F. Analysis of resistant starch: a method for foods and food products. Food Chemistry, v.56, n.4 , p.445-449, 1996), the levels of AR in products can be classified as: negligible (^ 1%), low (1 to 2.5%), intermediate (2.5 to 5%), high ( 5 to 15%) and very high (15%).

[0059] The determination of the water absorption index and water solubility index was carried out using the methodology described by Anderson et al. (Anderson, RA; Conway, HF; Pfeifer, VV; Griffin JR., EL (1969). Gelatinization of corn grits by roll and extrusion cooking. Cereal Science Today, 14 (1), 4-7.), With changes made by Schmiele (Schmiele, M. (2009). Characterization of the different grain sizes of toothed and hard corn and evaluation on the quality of expanded extrudates. 2009. 223f. Dissertation (Master in Food Technology) - Faculty of Food Engineering, Universidade Estadual de Campinas, Campinas). The analysis consists of weighing a 2.5 g sample on a dry basis, in 50 mL conical tubes, adding 30 ml of distilled water at 25 ° C and keeping the tubes under agitation for 30 minutes.

[0060] The suspension was centrifuged at 2200g per 10min in a centrifuge and the supernatant evaporated and dried in an oven with circulation and air renewal at 105 ° C for 4 hours. The results were calculated using the following equations:

17/35

ISA =

Mre Ma (bs) xlOO

IAA = ·

Mrc

Equation 1

Ma - Mre

Equation

-xlOO

Where:

ISA = water solubility index (%);

IAA = water absorption index (g of gel / g of sample);

Mre = Mass of the evaporation residue (g);

Ma = Mass of the sample (g), on a dry basis;

Mrc = Mass of the centrifuge residue (g).

[0061] The viscosity analysis was carried out in accordance with ICC method 162 (ICC International Association for Cereal Science and Technology. Rapid pasting method using the Newport Rapid Visco Analyzer. Standard 162, 1996).

A sample of 3.0 grams (with a base humidity of 14%) was weighed in the specific tube for analysis, added with 25 mL of water and evaluated through a temperature and agitation profile as described in Table 1.

Table 1 - Profile for viscoamylographic analysis in RVA (Rapid Visco Analyzer) for extruded starches with and without fatty acids

Time (min) Variable Value 00:00:00 Temperature 25 ° C 00:00:00 velocity 960rpm 00:00:10 velocity 160rpm 00:02:00 Temperature 25 ° C 00:07:00 Temperature 95 ° C 00:10:00 Temperature 95 ° C 00:15:00 Temperature 25 ° C 00:20:00 End of test End of test

[0062] The data analyzed were: Cold viscosity;

Cold viscosity area; Maximum hot viscosity; Drop in viscosity; Final viscosity; Tendency to retrogradation.

18/35 [0063] The product extruded with fatty acids had a resistant starch content of 7.10% and a digestible starch of 91.56%. The L parameter of the instrumental color had a value of 94.58, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. This product will contain about 7 q of AR / 100 g of product, which can be considered high content of AR

according to classification proposal per Goni et al. (1996). [0064] Solubility in Water of starch extruded was in 2.69% and an absorption in Water in 464% . The trend The

retrogradation of this starch was low (33, 67 cP). The data presented in Table 2 indicate that the starch is already gelatinized, as the raw starch is insoluble in water and does not absorb water, forming suspensions with water. The low tendency to retrogradation indicates that this starch can be used in food products without promoting the retrogradation of the starch gel. Retrogradation is an effect little appreciated by the consumer, since there is also the syneresis of water, as an example in soups and puddings containing starches that have been gelatinized by heating and that when they undergo cooling form layers of starch retrograded on the surface (soup) or fissures (pudding), with release of water that becomes free and suitable for microbial growth.

19/35

Table 2 - Results of the analysis of the experiments of the examples of ingredients from 2 to 12 &

§ and $ *>

Λί «f

Γ Γ- cn r * cn r- Γ i-4 The <P LP CM tp cn cn <P The CM Ό xT cn m O r * r * tn LP IP to t-4 The r4 k t0 k O * CO CO k t0 * tn O cn V0 O k 00 k k k k <0 k tn k CM k k * tn k CD k k k k k CM k m The 04 O CM cn cn cn cn -Φ o c4 XT cn <0 04 • M * tn CM O cn tO +1 tn + i CM +1 04 -H t-4 +1 tn -h r4 +1 CM Ή n 4-1 KP 44 cn 44 cn r4 r4 CO cn w O LP xr r4 O 0Ί O cn O CO O grandfather O fO H CM O O O φ k 04 - tn k «R k cn k tn - cn k cn k cn k CM k cn k k O ·. O k O k O k O w o k O k O k O k O k O +1 V -H -H v 44 v +1 v 44 xr +1 n * 44 xr +1 44 -H φ cn CM cn O cn cn LP 04 cn CM cn O r4 r4 cn O CM O r- T-f i-l O Γ O CO O O O r4 O cn O <0 k t4 * CD k w * k k CM * cn k r4 k cn k 04 k CO k k O * O k O k O k Q * O k O k O O k O k O 04 +1 04 44 i-4 +1 CM 44 CM +1 04 +1 r4 +1 cn 44 r4 +4 CM 44 i-4 44 W tn CM CM C0 O xf CM CM C0 cn cn tn CO i-4 G0 tn 1-4 r4 1-4 O O cn i-4 O CM CD 04 CM O cn O xr O xr O cn O k k 00 k k k k k k k k k cn k Φ s r- k r * k O Η O k O O O HI O O o O O k O k O k O k O r-4 +1 t-4 +1 <n H 1-4 Ή i-4 44 Ή r4 +1 cn 44 00 +1 cs 44 cn 44 LP cn The r4 04 LP cn V r4 04 tn CM O r4 CO r4 CO i-4 CO CM cn O cn o O O O O xr O cn o O O O O CO O tp O r4 O O O the o r4 O i-4 O i — 1 O the o O 1-4 O O O O O r4 O +1 1 +1 1 44 1 44 t 44 1 44 1 44 1 +1 1 44 1 4-1 1 44 00 O LP o <P LP r4 tn CM θ ' r * lp cn CM cn V ’Φ θ ' xr CO CM tn i-4 10 i-4 O O cn O r4 O ω h r- O O O CM O xr O TT O O cn o 10 O C0 O LP O cn o tn O <0 O <0 O tn O <0 O <n +1 cn + i cn +1 cn Ή cn Ή <n -η <n 44 <n -H cn +1 cn 44 cn 44 <sD r4 the CO tP iH LP cn CO Γ cm tn CM cn cn CM CM cn 04 O O 1-4 tn • Φ <p cn tP t4 xr xr w CM the r- tn CM O CM i-4 CM Γ tn 00 r4 OJ H o 04 tn LO CM O t-4 i-4 o M * O V i-4 CO O cn tn <n in Ή cn +1 CO +1 CO 44 cn +1 cn 44 C0 Ή CD 44 CO 44 CO Ή CD 4-1 O OJ CM O CO xr tn θ ' cn iH cn cn CO r4 tn r4 10 O CO tn o- r4 oo 04 O r « χΤ ςρ cn r4 tn xr tn tn O 00 CM r4 i-4 * O * O Φ O cn O k O * O M * φ Φ O O m k O θ ' Ή r + i <r4 44 r4 Ή to +1 Γ Ή i-4 +1 r4 +1 i-4 4-1 i-4 44 <n 4-1 O O V 10 <0 xr O O O xT <n r4 K0 <0 T4 cn tn cn r4 r4 t4 CM r4 1 CM r4 1-1 CM CM CM O tn O O O O tn tn tn O O O CM xr 'T r4 r4 04 04 CM i-4 tn O O O O O tn tn tn O O OJ O * 4 r4 CM 04 CM r4

& AP - Palmitic acid (C16); AE - Stearic acid (C18); ÜC Conditioning humidity; AR - Resistant starch; AD - digestible starch; Color in the Lab system, where: L - luminosity parameter of the instrumental color (ranges from 0 black to 100 white), a * - ranges from -60 (green) to +60 (red), and b * varies from -60 (blue) at +60 (yellow); ISA - water solubility index; IAA - water absorption index (g of gel / g of sample on a dry basis); IE - expansion index; VF Cold viscosity; Values correspond to the average of three repetitions ± standard deviation.

20/35

Example 3 [0065] Extrusion of corn starch added with 2.5% stearic acid and conditioned to 19% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final moisture below 15%, followed by crushing to a particle size below 250pm.

[0066] The extruded product had a resistant starch content of 7.05% and a digestible starch of 91.60%. The L parameter of the instrumental color had a value of 93.66, a value very close to the native starch which was 99.58%, as well as for the parameters a * and b * of the instrumental color.

[0067] The water solubility of the extruded starch was 2.11% and a water absorption of 424%. The cold viscosity, with the analysis of paste properties, formed by the sample was 65.67 cP (Table 2).

[0068] The results of this example showed that one can vary the process and obtain results similar to other processes, in this case, this example differs from example 3 by the modification of the fatty acid used, but results were obtained close to example 3, or whether it has a high AR content, it is a gelatinized starch, with high water absorption, with cold viscosity and low cooling retrogradation, indicating that they can be used as thickeners and / or instantaneous in food products, which are characteristics not found in starch crude.

21/35

Example 4 [0069] Extrusion of corn starch added with 4.0% palmitic acid, 4.0% stearic acid and conditioned to 21.4% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then, the product went through a drying process until final humidity below 15%, followed by crushing to a particle size below 250pm.

[0070] The extruded product had a resistant starch content of 16.12% and digestible starch of 86.66%. The L parameter of the instrumental color showed a value of 96.06, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 1.89% and a water absorption of 459%. The cold viscosity formed by the sample was high (206, 67 cP), as shown in Table 2.

[0071] There was an increase in the AR content, which can be considered a starch with a very high AR value, according to Goni et al. (1996). This product is pre-gelatinized, with high cold thickening capacity, as it has high values of cold viscosity and water absorption. Due to its white color and high luminosity, this starch can be used as an ingredient, without changing the color of food products, but increasing the fiber content.

Example 5 [0072] Extrusion of corn starch added with 4.0% palmitic acid, 4.0% stearic acid and conditioned to

22/35

16.6% humidity. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final moisture below 15%, followed by crushing to a particle size below 250pm.

[0073] The extruded product had a resistant starch content of 13.28% and digestible starch of 85.46%. The L parameter of the instrumental color showed a value of 96.31, a value very close to the native starch which was 99.58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 2.42% and a water absorption of 449%. The cold viscosity formed by the sample was high (295, 67 cP), as shown in Table 2.

[0074] This product was obtained with the variation in the process, where the humidity was reduced, however it presents the same behavior of example 4 (high moisture content), being a pre-gelatinized product and ready for consumption, being considered with high AR content.

Example 6 [0075] Extrusion of corn starch added with 1.0% palmitic acid, 1.0% stearic acid and conditioned to 16.6% humidity. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then, the product went through a drying process until final humidity below

23/35

15%, followed by crushing to a particle size less than 250pm.

[0076] The extruded product had a resistant starch content of 8.50% and digestible starch of 90.18%. The L parameter of the instrumental color showed a value of 96.12, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 2.47% and a water absorption of 438%. The cold viscosity formed by the sample was 132.33 cP (Table 2).

[0077] This product can be classified as high AR content and shows that with a decrease in the concentrations of fatty acids (in relation to the product of example 5) there was a decrease in the AR content. In this case, as in the other products in the previous examples, the product is pre-cooked and can be used as a thickener, with a color similar to native (raw) starch, but with high water absorption and cold viscosity; and can also be used in instant preparations or in products that will be subjected to heat treatment.

Example 7 [0078] Extrusion of corn starch added with 1.0% palmitic acid, 1.0% stearic acid and conditioned to 21.4% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final moisture below 15%, followed by crushing to a particle size below 250pm.

24/35 [0079] The extruded product had a resistant starch content of 7.64% and digestible starch of 91.02%. The L parameter of the instrumental color had a value of 93.67, a value very close to the native starch which was 99.58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 2.21% and a water absorption of 454%. The cold viscosity formed by the sample was 54.00 cP (Table 2).

[0080] This product can be considered as high AR content, pre-cooked and with high cold viscosity and high water absorption. Therefore, this instant pre-cooked starch contributes to the reduction of the caloric value of the starch and can be used as a thickener in products treated or not thermally.

Example 8 [0081] Extrusion of corn starch added with 2.5% palmitic acid, 2.5% stearic acid and conditioned to 19.0% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final humidity below 15% (w / w), followed by crushing to a particle size below 250 pm.

[0082] The extruded product had a resistant starch content of 14.33% and digestible starch of 84.42%. The L parameter of the instrumental color had a value of 95.79, a value very close to the native starch which was 99.58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was

25/35 of 1.97% and a water absorption of 434%. Ά cold viscosity formed by the sample was 115.67 cP (Table 2).

[0083] This product is classified with high AR content, pre-cooked and has high water absorption and high cold viscosity, being considered instantaneous. Therefore, this instant pre-cooked starch contributes to the reduction of the caloric value of the starch, and can be used through direct application, to thicken cold drinks or not, bakery products, among others.

Example 9 [0084] Extrusion of corn starch added with 2.5% palmitic acid, 2.5% stearic acid and conditioned to 15.0% humidity. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then, the product went through a drying process until final humidity below 15% (m / m), followed by crushing to a particle size below 250pm.

[0085] The extruded product had a resistant starch content of 14.53% and digestible starch of 84.23%. The L parameter of the instrumental color showed a value of 96.02, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 3.18% and a water absorption of 433%. The cold viscosity formed by the sample was 238.33 cP (Table 2).

[0086] This product is classified with high AR content and has characteristics of instant product, being pre-cooked, with high water absorption. So this starch

26/35 contributes to the reduction of the caloric value of starch, and can be used as a thickener, directly in drinks and other products, whether or not it can be heated.

Example 10 [0087] Extrusion of corn starch added with 2.5% palmitic acid, 2.5% stearic acid and conditioned to 23.0% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then, the product went through a drying process until final humidity below 15%, followed by crushing to a particle size below 250pm.

[0088] The extruded product had a resistant starch content of 10.48% and digestible starch of 88.22%. The L parameter of the instrumental color showed a value of 96.24, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 1.90% and the water absorption was 432%. The cold viscosity formed by the sample was 92.00 cP (Table 2).

[0089] This product is classified with high AR content, presenting characteristics of instant product, being pre-cooked, with high water absorption, therefore, this starch contributes to the reduction of the caloric value of the starch, it can be used as a thickener, with direct application in drinks and other products, whether or not it can be heated.

Example 11 [0090] Extrusion of corn starch added with 1.0% palmitic acid, 4.0% stearic acid and conditioned to

27/35

21.4% humidity. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then, the product went through a drying process until final humidity below 15%, followed by crushing to a particle size below 250pm.

[0091] The extruded product had a resistant starch content of 15.55% and digestible starch of 83.22%. The L parameter of the instrumental color had a value of 95.47, a value very close to the native starch which was 99.58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 2.21% and a water absorption of 424%. The cold viscosity formed by the sample was 65.57 cP (Table 2).

[0092] This product is classified with a very high content of AR, presenting characteristics of instant product, being pre-cooked, with high water absorption. Therefore, this starch contributes to the reduction of the caloric value of the starch, and can be used as a thickener, directly in drinks and other products, whether or not it can be heated.

Example 12 [0093] Extrusion of corn starch added with 4.0% palmitic acid, 1.0% stearic acid and conditioned to 21.4% moisture. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final humidity below

28/35

15%, followed by crushing to a particle size less than 250pm.

[0094] The extruded product had a resistant starch content of 9.18% and digestible starch of 89.50%. The L parameter of the instrumental color showed a value of 96.48, a value very close to the native starch which was 99, 58%, as well as for the parameters a * and b * of the instrumental color. The water solubility of the extruded starch was 1.89% and a water absorption of 431%. The cold viscosity formed by the sample was 302.67 cP (Table 2).

[0095] This product is classified with a high AR content and features instantaneous product, with high water absorption. Therefore, this instant pre-cooked starch contributes to the reduction of the caloric value of the starch, and can be used as a thickener directly in drinks and other products, whether or not it can be heated.

Example 13 [0096] Corn starch extruded for use as an ingredient, obtained from the extrusion of starch without fatty acids and with a mixture of 3.62% palmitic acid and 4.79% stearic acid, both with 20, 26% moisture content of the raw material. The samples extruded with the absence and presence of fatty acids were processed for comparison purposes, aiming to verify the effect of fatty acids in the final product. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until

29/35 final humidity less than 15% (m / m), followed by crushing to a particle size less than 250pm.

[0097] Figure 2 shows the levels of resistant and digestible starch in the samples. A significant increase in the resistant starch content is observed with the use of fatty acids, where the sample without the fatty acids presented a resistant starch content of 2.34% (considered resistant type 3 starch). With the use of fatty acids, the resistant starch content increased to 17.17%, and this increase (in relation to the sample without fatty acid) can be considered as formation of type 5 resistant starch.

[0098] Ά Figure 3 presents the data for the instrumental color and it appears that the tones are very similar, due to the very close values for the parameters L, a * and b *, indicating that there was no considerable color change that could change the color of the starch to be used as an ingredient. Figure 4 shows the values of the water solubility index and the water absorption index.

[0099] It was found that there was a decrease in both indices, as a result of the complexation of starch with fatty acids, decreasing the affinity of the material with water, since the fatty acids have a hydrophobic characteristic. In addition, the use of fatty acids may have acted as a lubricant within the extruder tube, resulting in a lower degree of shear, reducing the exposure of hydroxyl groups (responsible for the formation of hydrogen bonds with water) and also decreasing the dextrinization of the starch (formation of compounds of

30/35 lower molecular weight responsible for increasing water solubility).

[00100] Figure 5 shows the viscoamylographic curves of the samples, indicating a similar behavior in the effects of fatty acids to those observed in the absorption and water solubility indices. This product is classified with a very high content of AR, presenting characteristics of instant and pre-cooked product, with high water absorption. Therefore, this starch can contribute to the reduction of the caloric value of the final product, and can be used as a thickener, with direct application in drinks and other food products, whether or not it can be heated.

Example 14 [00101] Cassava starch extruded for use as an ingredient, obtained from the extrusion of starch without fatty acids and with the mixture of 3.62% palmitic acid and 4.79% stearic acid, both with 20, 26% moisture content of the raw material. The samples extruded with the absence and presence of fatty acids were processed for comparison purposes, aiming to verify the effect of fatty acids in the final product. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final humidity below 15% (m / m), followed by crushing to a particle size below 250pm.

[00102] Figure 6 shows the levels of resistant and digestible starch in the samples. There is a

31/35 significant increase in the resistant starch content with the use of fatty acids, where the sample without the fatty acids presented a resistant starch content of 3.81% (considered resistant type 3 starch). With the use of fatty acids, the resistant starch content increased to 13.28% (classified as high AR content, according to Goni et al. (1996)), and this increase (in relation to the sample without fatty acid) can be considered as formation of type 5 resistant starch. Figure 7 presents the data for the instrumental color and it is verified that the tones are very similar, due to the very close values for the parameters L, a * and *, indicating that there is no there was a considerable color change that could change the color of the starch for use as an ingredient. Figure 8 shows the water solubility index values and the water absorption index. It was found that there was an increase in the water absorption index with the use of fatty acids and a decrease in the water solubility index. Figure 9 shows the viscoamylographic curves of the samples. It was observed that the sample extruded with fatty acids showed higher values for all parameters. Figure 10 shows the infrared spectra of the samples, and the absence of the ester group band at 1740 cm ^-1 indicates that there was no reaction of esterification of starch with fatty acid.

[00103] This product is classified with a high AR content, presenting characteristics of instant and pre-cooked product, with high water absorption. Therefore, this starch can contribute to the reduction of the caloric value of the final product, and can be used as a thickener, with application

32/35 direct in beverages and other food products, which may or may not be heated.

Example 15 [00104] Sorghum starch extruded for use as an ingredient, obtained from the extrusion of starch without fatty acids and with the mixture of 3.62% palmitic acid and 4.79% stearic acid, both with 20, 26% moisture content of the raw material. The samples extruded with the absence and presence of fatty acids were processed for comparison purposes, aiming to verify the effect of fatty acids on the final product. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final humidity below 15% (m / m), followed by crushing to a particle size below 250pm.

[00105] Figure 11 shows the levels of resistant and digestible starch in the samples. A significant increase in the resistant starch content is observed with the use of fatty acids, where the sample without the fatty acids showed a resistant starch content of 3.61% (considered resistant type 3 starch). With the use of fatty acids, the resistant starch content increased to 15.03% (classified as very high AR content, according to Goni and al. (1996)), and this increase (in relation to the sample without fatty acid) can be considered as formation of type 5 resistant starch. Figure 12 presents the data for the instrumental color and it is verified that the tones are very similar, due to the values

33/35 very close for parameters L, a * and b *, indicating that there was no considerable color change that could change the color of the starch for use as an ingredient. Figure 13 shows the water solubility index values and the water absorption index. It was found that there was a decrease in both indices, as a result of the complexation of starch with fatty acids, decreasing the affinity of the material with water, since the fatty acids have a hydrophobic characteristic.

[00106] In addition, the use of fatty acids may have acted as a lubricant inside the extruder tube, resulting in a lower degree of shear, reducing the exposure of hydroxyl groups (responsible for the formation of hydrogen bonds with water) and also decreasing the dextrinization of starch (formation of lower molecular weight compounds responsible for increasing water solubility). Figure 14 shows the viscoamylographic curves of the samples. It was observed that the sample extruded with fatty acids showed higher values for all parameters. Figure 15 shows the infrared spectra of the samples, and the absence of the ester group band in 17 40 cm ^-1 indicates that there was no reaction of esterification of starch with fatty acid.

[00107] This product is classified with a very high content of AR, presenting characteristics of instant and pre-cooked product, with high water absorption, therefore, this starch can contribute to the reduction of the caloric value of the final product, and can be used as thickener, with

34/35 direct application in beverages and other food products, which may or may not be heated.

Example 16 [00108] Corn starch with high amylose content (Himaize type) extruded for use as an ingredient, obtained from the extrusion of starch without fatty acids and with the mixture of 3.62% palmitic acid and 4.79 % stearic acid, both with 20.26% moisture content of the raw material. The samples extruded with the absence and presence of fatty acids were processed for comparison purposes, aiming to verify the effect of fatty acids on the final product. The process temperatures were 80, 120 and 160 ° C, corresponding to I ^a , 2 ^a and 3 ^the heating zone, screw speed of 120 rpm, feed flow of 8 kg / h and matrix with 30 mm ² opening. Then the product went through a drying process until final moisture below 15%, followed by crushing to a particle size below 250pm.

[00109] Figure 16 shows the levels of resistant and digestible starch in the samples. It is observed that there is no difference in the resistant starch content with the use of fatty acids, where the sample without the fatty acids presented a resistant starch content of 30.13% ((classified as very high AR content, according to Goni and (1996)). With the use of fatty acids, the resistant starch content showed a small increase to 33.79%, and this increase (in relation to the sample without fatty acid) can be considered as formation of resistant starch type 5. Figure 17 presents the data for the instrumental color and it appears that the tones are very

35/35 similar, due to the very close values for parameters L, a * and b *, indicating that there was no considerable color change that could change the color of the starch to be used as an ingredient.

[00110] Figure 18 shows the values of the water solubility index and the water absorption index. It was found that there was no significant change in both values, indicating that the use of fatty acids had no effect on these properties. Figure 19 shows the viscoamylographic curves of the samples. It was observed that the sample extruded with fatty acids showed lower values for all parameters. Figure 20 shows the infrared spectra of the samples, and the absence of the ester group band at 1740 cm ^-1 indicates that there was no reaction of esterification of starch with fatty acid.

1/3

Claims (12)

1. Process of obtaining mixed resistant starch of type 3 and type 5 pre-gelatinized characterized by comprising the following steps: a) Mix and homogenize at least one fatty acid to starch, in a concentration of one to ten percent, considering each isolated fatty acid or the sum between the combinations; b) Means for adjusting the humidity of the resulting mixture in step (a) until a humidity range of 14 to 25% (w / w) is obtained, preferably 20% (w / w); c) Extrude in a thermoplastic extruder at temperatures between 80 and 170 ° C with gradual heating from the feed end to the end of the die, and a minimum screw rotation speed of 80 rpm; d) Obtain the mixed resistant starch of type 3 and 5 pregelatinized. 2. Process, according to claim 1, characterized by the fact that in step (a) the starch is selected from the group comprising cereals, roots, tubers or stems, preferably corn starch, which can be normal, waxy or with high amylose content. 3. Process, according to claim 1, characterized by the fact that in step (a) the fatty acid is selected from the group comprising lauric, myristic, palmitic and stearic. 4. Process, according to claim 1, characterized by the fact that in step (a) preference is given to 2/3 mixture of palmitic acid with stearic acid in a ratio of 4: 6, respectively. 5. Process according to claim 1, characterized in that in step (a) the concentration of at least one fatty acid is preferably five percent. 6. Process according to claim 1, characterized in that in step (b) the means for adjusting the humidity comprise adding water, adding water vapor, or drying or any other means that allows to reach the humidity of 14 at 25% (w / w). Resistant starch characterized in that it is obtained according to claims 1 to 6. 8. Process according to claims 1 to 6, characterized in that it optionally comprises a drying step to humidity below 6% (w / w). Process according to claim 8, characterized in that it optionally comprises a covering or dredging step to fix aromas and flavors. 10. Use of the products obtained according to the process described in claims 8 and 9, characterized by the fact that it is intended for direct consumption as breakfast cereal or snacks. 11. Process according to claims 1 to 6, characterized in that it optionally comprises a step of adjusting the humidity until the product obtained in step (d) has a humidity of less than 15% (w / w), and grind to a particle size of powder. 12. Use of products obtained according to the process described in claim 11, characterized by the fact that it is applied 3/3 to obtain thickening or water retention without using heat in puddings, soups, broths, instant milk mixes and breakfast foods; to prepare ready-made bread mixes; for use as a binder in the meat industry; for filling fruit tarts. 1/14 expansion index expansion index Afrwdode corn «toned $ emAG BComAC (a) expansion index 3.1S Sorghum starch exbuished Without AO * With AO (C)