RU2311798C2 - Method for regulating the content of glucose and providing its regulated supply and dietary product for its implementation - Google Patents

Abstract

FIELD: dietology.

SUBSTANCE: the suggested dietary product contains inhibited starch with supplemented bound phosphorus at the quantity ranged 0.10-0.35%. Starch provides digestion of under 25% starch/20 min, 30-70%/120 min and above 60%/240 min at measuring according Englist's technique, moreover, it contains under 40% amylose. Such starches being the constituents of dietary products provide a consumer with glucose for prolonged period of time and at more constant level .

EFFECT: higher efficiency of regulation.

15 cl, 2 dwg, 4 ex, 3 tbl

Description

This application has priority application US Ser. No. 60/591997, filed July 29, 2004

The present invention relates to the use of (cross-linked) cross-linked or inhibited starch for controlling and / or regulating blood glucose levels. Such starches control and / or regulate the level of glucose in the blood of mammals when they are used as a food or feed source by changing the time and rate of absorption after consumption.

Starch is the main source of energy in a typical Western diet. Refined starches (see the description of refined starches made by Imberty et al. Die Starke, 43 (10), 375-84 (1991)) are mainly consumed in cooked form, usually causing a high and sharp rise in blood glucose levels as a result of rapid and complete digestion. However, some refined starches are able to withstand enzymatic hydrolysis in the small intestine in such a way that the starch is essentially not broken down until it reaches the large intestine, where it is utilized by permanent microorganisms (such starch is called resistant starch or RS). Englyst (Englyst, H.N .; et al. Eur. J. Clin. Nutr. 46 (suppl.2): S33-S50, 1992) identified three different categories of resistant starches based on their source and resistance properties. Brown later described the fourth type of RS (Brown et al. Food Australia, 43 (6), 272-75 (1995)), including chemically modified starches containing ethers, esters and crosslinked enzymes that are resistant to enzymatic digestion.

The term “available carbohydrate” means the total amount of carbohydrates in food minus the amount of non-digestible carbohydrates. Non-digestible carbohydrates include dietary fiber, sugar alcohols and indigestible sugars. A wide class of dietary fiber includes a group of the aforementioned starches described by Anglist and Brown (RS1-4). According to some published examples, resistant starch is measured or quantified as dietary fiber (eg Chui et al. US Pat # 5902410) using standard methods of determination (see AOAC 985.29 and 991.42), while the starch does not cause or causes the formation of small or zero the amount of absorbed consumed glucose fermented in the colon. In addition, the presence of resistant starch affects the amount of available carbohydrates in food, playing the same role as dietary fiber (e.g. cellulose, inulin, psylium and bran), and affecting the amount of available carbohydrates.

Glycemic reaction (GR) refers to the effect of different products on blood glucose levels over a period of time from 0 to 120 minutes (NIH Publication Number 99-3892, 1999). It is measured as a gradually increasing area under the curve of blood glucose in an individual subject in response to a specific product sample on a particular day. The volume and duration of the glycemic reaction to various types of products reflects the variability of the speed and level of digestion and absorption of glucose-containing components such as starch. The mentioned method is used to determine the reaction volume for sugar after taking a certain product, as well as to compare (relative glycemic reaction) of different products using the same sample or volume. It is applicable to determine the effect on blood glucose of various foods consumed by humans and animals.

According to this application, the glycemic index (GI) (Jenkins, DJA et al., Am. J. Clin. Nutr. 34 (3): 362-66, 1981) is defined as “a gradually increasing area under the curve of blood glucose in response 50 g portion of available carbohydrates in the test product and expressed as a percentage of the reaction to the same amount of available carbohydrates in a standard portion of the product consumed by the same subject. " For a standard portion of the product, an arbitrary value of 100 was taken, which can be either 50 g of glucose or 50 g of white bread.

GI helps to quantify the interaction of various product ingredients and their role in digesting the carbohydrate source and glucose absorption. To provide the indicated amount of available carbohydrates (50 g) in the test product, you need to eat more (sometimes much more) of the test product. In other words, the consumed portion of a product rich in fats, protein or fiber should be larger in order to ensure the intake of the necessary 50 g of available carbohydrates.

After consumption of the product, two main mechanisms act on the glucose contained in the blood. The first mechanism is the rate of absorption of glucose into the bloodstream as the product is digested. The second mechanism is the rate of absorption of glucose from blood into body tissues. Despite such a simplified description of the two mechanisms mentioned, one skilled in the art understands the complex and multifaceted nature of the mechanisms, reactions, and processes involved. The body of normal healthy individuals has mechanisms that regulate blood glucose in a certain framework (American Diabetes Association, Diabetes Care, 24 (suppl), 1-9 (2001) sets fasting plasma glucose from 3.9 to 6.1 mmol / l). For example, an increase in blood glucose stimulates the production of insulin, which, among other functions, facilitates the absorption of glucose into the tissue, and also plays a major role in the metabolism of fats and proteins. Therefore, a product that causes a sharp increase in blood glucose concentration causes a rapid (but time-shifted) increase in serum insulin, which leads to the absorption, accumulation and use of glucose by muscle cells, adipose tissue and the liver, thereby regulating the concentration of glucose in the blood “Normal” range.

Tissue-absorbed glucose can be converted to glycogen as a storage medium in muscles. Glycogen is consumed during physical activity and replenished during rest. Athletes use a carbohydrate load to increase energy reserves (in the form of glycogen) in the muscles before sports. This is “a strategy in which changes in training and nutrition can maximize muscle glycogen storage before endurance competition” (Michelle Minehan, AIS Sports Nutrition Program, 2003). Glycogen can also be transported from muscle to the blood to increase blood glucose when it falls below a certain level.

A number of conditions are associated with excessive / insufficient production of insulin or the reaction of cells in the body to actions usually initiated by insulin. Insulin resistance (IR) is a condition in which body tissue becomes less susceptible to insulin and requires more in order to have the same physiological effect. The primary effect of IR has been defined as a decreased level of glucose utilization by body cells, leading to increased mobilization of fats in fat accumulation sites and a decrease in protein in body tissues (Guyton, AC "Textbook of Medical Physiology" (7 ^th Ed.), WB Saunders Company : Philadelphia, Pa. 923-36). Other conditions resulting from excessive / insufficient insulin production include hypoglycemia, hyperglycemia, poor glucose regulation, insulin resistance syndrome, hyperinsulinemia, dyslipidemia, dysfibrinolysis, metabolic syndrome, X syndrome and diabetes mellitus (type II, also known as non-insulin-dependent diabetes mellitus (NIDDM), as well as the physiological conditions they cause, such as cardiovascular disease, retinopathy, nephropathy, peripheral neuropathy, and sexual dysfunction.

Another result often associated with a rapid rise and sharp fluctuations in blood glucose is the inability to control and maintain body weight. Insulin, which has many functions in the body, is also active in converting glucose to fat (Anfisen et al. US Published Application No. 2004/0043106). It is believed that insulin resistance, necessitating a high serum insulin content, is the reason for gaining weight, since increased insulin levels contribute to excessive fat accumulation. Specialists have long been recommending consuming food in small portions throughout the day to regulate blood glucose (and the corresponding energy supply) at a constant and uniform level. In addition, it was found that the rapidly falling blood glucose (which usually occurs after a sharp rise) stimulates appetite (hunger) in healthy adults. Alternatively, studies show that glucose release over a long period of time provides specific benefits, which may include a higher degree of saturation for longer periods of time (weight regulation such as weight loss and its long-term stabilization), prolonged energy release (enhanced sports activities, including training), as well as improving mental concentration and memory.

Starch or a starch-rich material that can provide blood with glucose for an extended period of time serves to maintain a normal / healthy blood glucose level (i.e., normoglycemia) and reduce / prevent rapid changes in blood glucose levels. It is a very good source of carbohydrates in the prevention and treatment of any of the above conditions. Healthy people who want to control the release of glucose or regulate the release of energy from food, as well as to prevent or treat many diseases associated with changes in blood glucose and insulin levels, can eat foods containing such starches.

Surprisingly, crosslinked or inhibited starches have been found to be able to control and / or regulate the blood glucose of mammals after their consumption and subsequent absorption. It has also been found that such crosslinked or inhibited starches, appropriately included in food products or used as additives, can provide controlled and / or controlled glucose levels in the blood of a consumer over a long period of time.

The present invention relates to the use of crosslinked or inhibited starch for controlling and / or regulating glucose content from foods or food additives after their consumption (i.e., after their absorption). Such starches include starches obtained by processing natural starch or starch-rich materials, such as flour or cereals, using methods known in the art for crosslinking or inhibiting starch, for example, starch treated with sodium trimetaphosphate and / or sodium tripolyphosphate. Such crosslinked or inhibited starches can reduce the initial sharp increase in blood glucose and, appropriately included in food products, can provide consumers with controlled / regulated blood glucose levels over an extended period of time, as well as contribute to a normal / healthy glucose content in blood even in individuals with insulin resistance.

As used herein, the term “granular” means non-gelatinized or dispersed by any chemical or physical method. Granular starches can be determined by microscopy by the presence of birefringence (Maltese cross) under polarized light. Granular starches are also not substantially soluble in water below their gelatinization temperature. Non-granular starches are starches processed to give them a high solubility in water (CWS) below their gelatinization temperature (typically around 65 ° C). Some starches can be processed to give them solubility, and then returned to their original state (subjected to retrograde) so as to obtain particles (crystallites) that no longer dissolve in water at temperatures below 100 ° C, but are also not granular. In one embodiment of the invention, a granular form of starch is used.

According to most researchers and publications, two time periods are chosen to measure carbohydrate digestibility. These periods are 20 and 120 minutes after ingestion or after the start of enzymatic digestion for in vitro methods, but do not accurately reflect their absorption in the stomach and small intestine. For this application, the digestion of various samples was measured after 20, 120 and 240 minutes in order to better understand the true physiological effect produced by these samples in the digestive system of mammals.

As used herein, the term “rapidly digestible starch” means starch, or parts thereof, that are completely absorbed within the first 20 minutes of their consumption and determined by a sharp increase in blood glucose concentration (Englyst et al., Eur. J. Nutr. 46 (suppl.2 ), s33-s50).

As used herein, the term “resistant starch” means starch or a portion thereof that is not digestible in the small intestine.

The term “slowly digestible starch” means starch or part thereof, which is neither fast-digesting starch nor resistant starch. In other words, slowly digestible starch is any starch that gives a substantial part of its glucose to the body of a mammal throughout its stomach and small intestine (in humans, as a rule, within 20 to 240 minutes). Such starches are described in more detail by Englyst et al., European Journal of Clinical Nutrition, 1992, 46, S33-S50. (Note: An Englist describes slowly digestible starches as starches that release glucose for 20-120 minutes, not 20-240 minutes).

As used herein, the term “bound phosphorus” refers to bound phosphorus as determined by the test described in the Examples section, and the phrase “added bound phosphorus” means bound phosphorus not naturally present in starch but added by chemical or other means. Therefore, the amount of added phosphorus is determined by subtracting the amount of phosphorus bound from the unmodified starch base from the amount of modified starch.

Figure 1 is a graph of the ideal slow release of glucose compared to normal starches, as well as the ideal release of glucose from a product containing such starches.

Figure 2 is a graph of the actual glucose release of raw corn starches crosslinked to varying degrees using STPP / STMP.

The present invention relates to the use of crosslinked or inhibited starch for controlling and / or regulating the level of glucose in the blood of mammals and its subsequent absorption. Such starches are obtained by treating natural starch or starch-rich materials, such as flour or cereals, using methods known in the art for crosslinking or inhibiting starch, for example, sodium trimetaphosphate (STMP) and / or sodium tripolyphosphate (STPP). Such crosslinked or inhibited starches, appropriately included in food or taken as a dietary supplement, can be used to produce a more constant level of glucose in the blood of the consumer (to prevent or minimize a sharp increase) over a long period of time (corresponding to the period during which the material is in the stomach / small intestine) than the level provided by other types of starches. Such starches and types of products containing the above-mentioned starches help the consumer regulate and maintain a normal and healthy blood glucose level.

As used herein, the term “starch” means all kinds of starch, flour and starch-containing materials obtained from tubers, grains, beans and seeds or any other natural source, each of which is suitable for use in the present invention. The term "natural starch" in this invention means starch that exists in nature. Also suitable are starches obtained from a plant grown using standard selection, including hybridization, translocation, inversion, transformation, or some other method of genetic or chromosome engineering, including their varieties, commonly called genetically modified organisms (GMOs). In addition, starch obtained from a plant grown as a result of artificial mutations (including plants grown from chemical mutagens) and variants of the above generic composition, which can be obtained by known standard methods of mutational selection, can also be used in this invention.

Common sources of starches are cereals, tubers, roots, beans and fruits. A natural source can be corn (maize), peas, potatoes, sweet potatoes, bananas, barley, wheat, rice, oats, sago, amaranth, tapioca (cassava), arrowurut, canna, triticale and sorghum, as well as waxy (low amyloid) them varieties. Particularly useful sources include maize, potatoes, cassava and rice. As used herein, the term “waxy” or “low amylose” means starch containing not more than about 10%, specifically not more than about 5%, most specifically not more than about 2 wt.% Amylose. The described invention relates to all types of starches and includes all sources of starches, including natural, genetically modified or obtained as a result of hybrid selection. However, high amylose starches, i.e. starches containing more than 40% amylose are not suitable in the present invention.

The starch of this invention can be obtained by treating natural starch or starch-rich materials with multifunctional (i.e., bifunctional) crosslinking agents, or by exposing the starch to an inhibition process. In one embodiment, the reagent is selected from the group consisting of sodium trimetaphosphate, sodium tripolyphosphate, and combinations thereof. Such crosslinked modifications are known in the art and are described, for example, in Modified Starches: Properties and Uses, Ed. Wurzburg, CRC Press, Inc., Florida (1986). One skilled in the art will recognize that by varying reaction conditions and reagents, the level and ratio of disubstitution and monosubstitution can be varied. How this ratio affects the rate of digestion and absorption into the body depends on many factors, including the type of starch, the amylose content and the granular composition / conformation, as well as the type of reagent and reaction conditions. The rate of digestion also depends on the method of cooking and the individual’s reaction to such food, including differences in the biochemistry and physiology of each individual.

The degree of crosslinking depends, among other things, on starch, a crosslinking agent, and how starch is consumed — whether cooked or raw. When using a crosslinking agent such as STMP, the degree of crosslinking is measured by the content of bound phosphorus, which according to the invention is present in a slowly digestible effective amount. In one embodiment, the amount of bound phosphorus is from 0.10 to 0.35%. When using other methods of inhibiting starch, alternative methods must be used to determine the effectiveness of the reaction and the level of inhibition.

Starch can be further modified to obtain the desired texture and / or physical properties. Additional modification may be carried out before or after crosslinking / inhibition, depending on the type of additional modification. The person skilled in the art knows what combinations are possible and in what order such a modification can be implemented. Additional modifications may include molecular weight reduction such as acid conversion or enzymatic treatment, substitution with propylene oxide (PO), ethylene oxide (EO), octenyl succinic anhydride (OSA), acetylation, oxidation and dextrinization.

The above modifications are usually carried out in an aqueous medium, in some way controlling or adjusting its pH. An experienced practitioner will easily pick up various materials and equipment for carrying out such reactions. An overview of the conditions for such reactions is given in Modified Starches: Properties and Uses, Ed. Wurzburg, CRC Press, Inc., Florida (1986), chapter 4. Other reaction media and conditions may also be used to provide materials within the scope of this invention. Such reactions and conditions include, but are not limited to, reactions using dry heat, solvents, supercritical fluids, and reactions in a gaseous atmosphere.

Starches can be modified in a granular state or after gelation using methods known in the art. Such methods include methods described, for example, in US patent No. 4465702, 5037929, 5131953 and 514999. See also Chapter XXII- "Production and Use of Pregelatinized Starch", Starch: Chemistry and Technology, Vol.III-Industrial Aspects, RL Whistler and E.F. Paschall, Editors, Academic Press, New York 1967.

The starches of the invention can be converted, for example, fluid or liquid boiling starches obtained by oxidation, acid hydrolysis, enzymatic hydrolysis, thermal and / or acid dextrinization. Such methods are well known in the art.

Starch can be cleaned by any method known in the art to rid it of odors, paints, eliminate microbial contamination, ensuring the safety of a food product or other undesirable components inherent in starch or formed during processing. Suitable purification methods in the processing of starches are described in the patent family presented by EP 554818 (Kasica et al.). The alkali washing methods described in the patent family of US Pat. Nos. 4,477,480 (Seidel) and 5,187,272 (Bertalan et al) may also be used. Starch can be purified by enzymatic removal of proteins. Reaction contaminants and by-products can be removed by dialysis, filtration, centrifugation, or any other method used in the art to isolate and concentrate starch formulations. Starch can be washed using known methods of removing soluble, low molecular weight fractions, such as mono- and di-saccharides and / or oligosaccharides.

The pH of the resulting starch is usually adjusted to the desired level in accordance with its intended end use. Typically, the pH is adjusted to a level of from 3.0 to about 6.0. In one embodiment, the pH is adjusted to a level of from 3.5 to about 4.5 using methods known in the art.

Starch can be regenerated using known methods, including, without limitation, filtration or drying, including spray drying, freeze-drying, drying in a stream of hot air or natural drying.

The resulting starch has an altered digestion profile such that less than 25% of the starch is digested within the first 20 minutes, according to another embodiment, less than 20% of the starch is digested. In one embodiment, starch is digested by less than 20%, and in another embodiment, less than 10% in the first 20 minutes.

In addition, the resulting starch is digested by 30-70% within 120 minutes after ingestion. In one embodiment, the starch is digested at least 40-60% within 120 minutes after ingestion, and in another embodiment, at least 45-55% within 120 minutes.

In addition, the resulting starch is digested at least 60% within 240 minutes after ingestion. In one embodiment, the starch is digested at least 70% within 240 minutes after ingestion; in another embodiment, the starch is digested by at least 80% within 240 minutes, and according to another embodiment, the starch is digested by at least 90% within 240 minutes.

One skilled in the art will appreciate that cooking starch affects the digestibility and rate of absorption of glucose into the blood. An overview of the cooking results is described by Brown, M.A., et al. British Journal of Nutrition, 90, 823-27 (2003).

According to a recent patent application by Brown et al., US 2003/0045504 A1, published March 6, 2003 and incorporated herein by reference, the relationship between resistant starch and other components of the products, such as various lipids, affects the digestibility, glycemic index (GI ), glycemic reaction (GR) and blood glucose level.

Starch is rarely consumed as such; it is usually consumed as an ingredient in a food product. Such a food product may be formulated with the aim of obtaining the desired glucose release curves. In one embodiment, the product is designed to produce a substantially zero order glucose release curve to provide a substantially constant and maintained glucose release rate.

Starch or starch-rich materials, such as flour, can be consumed raw, but are usually consumed after cooking and / or other processing. Therefore, it is contemplated that the present invention includes such starches that, after being added to the product and cooked, are capable of altering the glucose release curve. In one embodiment, the processed starch containing product contributes to a substantially zero order glucose release curve, providing a substantially constant and sustained glucose release rate. These types of products are modeled by the methods described in the Examples section below.

Crosslinked starch according to the invention does not cause a strong and rapid increase in blood glucose levels characteristic of starches with a high glycemic index, such as most natural starches, but, on the contrary, provides a more moderate increase over the baseline, which lasts for a long period of time . It also tolerates processing well, without causing a strong and rapid increase in blood glucose levels after ingestion of a product containing such starch, while the release of glucose from the prepared and / or processed product is essentially constant.

Crosslinked or inhibited starch according to the invention can be used in a wide variety of food products, including, without limitation: baked goods, including crackers, various types of bread, pastries, bagels, biscuits, cookies, pies and muffins; cereals, bars, pizza, noodles, sauces, including fluid sauces and sauces, topped with a spoon, pie fillings, including fruit and cream toppings; gravy, including white gravy and dairy gravy, such as cheese sauce, meat gravy, light syrups; puddings; custards; yoghurts; sour cream; drinks, including drinks based on milk, glaze; seasonings; confectionery and chewing gums; as well as soups.

It is contemplated that food products also include wholesome foods and beverages, including nutritional supplements, diabetic foods, sustained release foods such as sports drinks, nutrition bars, and energy bars.

Crosslinked or inhibited starch can also be used in various animal feed products, in young animal feed formulations providing the desired growth and development of such animals, in pharmaceutical formulations, nutritional products, over-the-counter (OTC) preparations, tablets, capsules, and other known excipients for the delivery of drugs intended for humans and / or animals, and / or for any other purpose, the achievement of which can be achieved by the continuous release of glucose and h the composition of the product.

Crosslinked or inhibited starch may be added in any desired or necessary amount to ensure the functionality of the composition. In one embodiment, starch may be added in an amount of from 0.01% to 99% by weight of the composition. In another embodiment, starch is added in an amount of from 1 to 50% by weight of the composition. Such starch can be added to the food product or drink in the same way as any other starch, usually by directly mixing with the product or adding to it in the form of Zola. The food product may contain additional components, such as water.

Food products can be prepared using the crosslinked or inhibited starch of the invention to achieve a substantially zero order glucose release rate. Such products are able to provide consumers with glucose for a long period of time and a more constant level of glucose in the blood.

Products that control and / or regulate the rate and volume of glucose absorption can saturate for longer periods of time and thus contribute to weight control. They are also able to provide a sustained release of energy and thus improve athletic performance, including training, as well as help improve concentration and memory.

Such products may also have pharmaceutical effects, including reducing the risk of developing diabetes, treating obesity, reducing or regulating weight, and providing prophylaxis or treatment for hyperglycemia, insulin resistance, hyperinsulinemia, dyslipidemia, and dysphibrinolysis.

EXAMPLES

The following examples are intended to further illustrate and explain the present invention and should in no way be construed as limiting. All percentages are given on a weight basis (w / w).

In the following examples, the following research methods were used:

Imitation of digestion - (Englyst et al., European Journal of Clinical Nutrition, 1991, 46, S33-S50)

Product samples were ground / milled, as if chewing. Samples of powder starch were sieved to a particle size of 250 microns or less. 500-600 mg ± 0.1 mg of the sample was weighed and placed in a sample tube. 10 ml pepsin (0.5%), guar gum (0.5%) and HCl solution (0.005 M) were added to each tube.

Tubes with control solution and standard glucose solution were prepared. The control solution was 20 ml of a buffer solution containing 0.25 M sodium acetate and 0.02% calcium chloride. Standard glucose solutions were prepared by mixing 10 ml of sodium acetate buffer (described above) and 10 ml of a 50 mg / ml glucose solution. Standard solutions were prepared in duplicate.

A mixture of enzymes was obtained by adding 18 g of pork pancreatin (Sigma P-7545) to 120 ml of deionized water, mixed well, and then centrifuged at 3000 g for 10 minutes. The supernatant was collected and 48 mg dry invertase (Sigma I-4504) and 0.5 ml AMG E (Novo Nordisk) were added to it.

Sample tubes were preincubated at 37 ° C for 30 minutes, then removed from the bath and 10 ml of sodium acetate buffer was added along with glass / marble beads (to improve physical destruction of the sample during shaking).

To the samples, control solution and standard solutions was added 5 ml of a mixture of enzymes. The tubes were shaken horizontally in a water bath at 37 ° C with a frequency of approximately 180 beats / min. The time "zero" represents the time the first addition of the mixture of enzymes in the first tube.

After 20, 120 and 240 minutes, 0.5 ml aliquots were taken from incubated samples and placed in a separate tube with 20 ml of 66% ethanol (to terminate the reaction). After an hour, an aliquot was centrifuged at 3000 g for 10 minutes.

The glucose content in each tube was measured using the glucose oxidase / peroxidase method (Megazyme Glucose Assay Procedure GLC 9/96). This method is colorimetric.

The degree of digestion of starch was determined by calculating the glucose content against glucose standards using a conversion coefficient of 0.9. The results are presented as “% digested starch” (calculated on dry weight) after 20, 120 and 240 minutes. The experimental error of this test was defined as ± 4.

Each batch of sample analyzes included a comparative sample of raw corn starch. The accepted range of% digestion of corn starch was as follows:

Time (minutes) twenty 120 240 Sample 1 (control) ¹ 18 ± 4 80 ± 4 90 ± 4 ¹ Melogel® Starch is a corn starch manufactured by National Starch and Chemical Company, Bridgewater, NJ, USA.

Associated Phosphorus Analysis

A 1.7% suspension of starch in a 5% EDTA solution was prepared, mixed for 5 minutes and filtered. The sample was washed four times on a filter with 200 ml of deionized water. Dry the sample at room temperature. A 3% suspension of starch in 4N HCl was quantitatively prepared, cooking stones were added, the sample was boiled for 7 minutes, cooled to room temperature, quantitatively diluted with deionized water and centrifuged to remove any possible microparticles. The sample was then analyzed for phosphorus using inductively coupled plasma spectrometry (ICP), using a standard analysis method to obtain the total amount of bound phosphorus. The added amount of bound phosphorus was determined by subtracting the total amount of bound phosphorus from the amount of modified phosphorus.

Cookies / biscuit food system model

The technique described below was used to simulate the process of obtaining cookies.

Measured moisture in the studied starch by gravimetric method.

The amount of additional water required to bring the moisture content in the starch to 25% (w / w) was calculated, which is a typical moisture content for a dough intended for baking cookies and biscuit.

50 g of starch was weighed into the bowl of the Sunbeam Mixmaster, the mixing blades were lowered into the bowl and the “mixing” was turned on.

They began to add a predetermined amount of water by spraying water on starch while stirring to evenly distribute moisture. Within 5 minutes, the addition of water was completed; continued mixing at the same speed until the starch ceased to adhere to the walls of the bowl. The total mixing time was 8-10 minutes.

Transferred 50 g of hydrated starch to an aluminum container (145 mm × 120 mm × 50 mm) and evenly distributed so that the entire bottom of the container was covered.

The furnace was preheated to 190 ° C.

The hydrated starch was heated at 190 ° C. for 120 minutes.

Starch was removed from the oven, immediately placed in a plastic container with a volume of 4 ounces (118.3 ml) and covered with a lid.

The starch was cooled to room temperature and the moisture content in the prepared starch was determined by gravimetric method. The moisture content in the prepared starch was 5-8% (wt./weight.), Which is common for cookies and biscuits.

The level of glucose release from starch was immediately determined or stored in an airtight container for testing the next day.

Example 1 - Preparation of Crosslinked Starches

Sample 1 - control corn starch - Melogel® starch manufactured by National Starch and Chemical Company, Bridgewater, NJ, USA.

Sample 2 - 3000 ml of tap water was measured in a reaction vessel. With stirring, 100 g of Na ₂ SO _{4 was} added and stirred until dissolved. With vigorous stirring, 2000 g of corn starch was added, and then the required amount of 3% NaOH was added dropwise to the suspension to obtain 40 ml of alkalinity (in fact 667 g of NaOH for 44.00 ml of alkalinity). The suspension was stirred for one hour and the pH was recorded (pH 11.71). The temperature was set at 42 ° C. 160 g of 99/1 STMP / STP mixture was added and reaction continued for 4 hours. The final pH and temperature were recorded (pH 11.02 and 42 ° C). The pH was adjusted to 5.5 using 3: 1 HCl (pH 5.49 after adding 164.99 g of HCl). The resulting starch precipitate was filtered and washed twice with 3000 ml of tap water. The precipitate was crushed and dried in the open.

Sample 3 - 3000 ml of tap water was measured into a reaction vessel. With stirring, 100 g of Na ₂ SO _{4 was} added and stirred until dissolved. With vigorous stirring, 2000 g of corn starch was added, and then the desired amount of 3% NaOH was added dropwise to the suspension to obtain 40 ml of alkalinity (667 g of NaOH for 44.00 ml of alkalinity). The suspension was stirred for one hour and the pH was recorded (pH 11.69). The temperature was brought to 42 ° C. 160 g of a 99/1 STMP / STPP mixture was added and reaction continued for 17 hours. The final pH and temperature were recorded (pH 11.32 and 42 ° C). The pH was adjusted to 5.5 using 3: 1 HCl (pH 5.57 after adding 146.88 g of HCl). The resulting starch precipitate was filtered and washed twice with 3000 ml of tap water. The precipitate was crushed and dried in the open.

Sample 4 - 3300 ml of tap water was measured in the reaction vessel. With stirring, 110 g of Na ₂ SO _{4 was} added and stirred until dissolved. With vigorous stirring, 2200 g of corn starch was added, and then the desired amount of 3% NaOH was added dropwise to the suspension to obtain 40 ml of alkalinity (733 g of NaOH for 44.14 ml of alkalinity). The suspension was stirred for one hour and the pH was recorded (pH 11.71). The temperature was brought to 42 ° C. 220 g of 99/1 STMP / STPP mixture was added and reaction continued for 17 hours. The pH was maintained using a controller and 3% NaOH (consumption was 556.6 g). The final pH and temperature were recorded (pH 11.19 and 42 ° C). The pH was adjusted to 5.5 using 3: 1 HCl (pH 5.49 after adding 285.38 g of HCl). The resulting starch precipitate was filtered and washed twice with 3300 ml of tap water. The precipitate was crushed and dried in the open.

Sample 5 - 2500 pounds (1134 kg) of tap water was measured in the reaction vessel. With stirring, 100 pounds (45.4 kg) of Na ₂ SO _{4 was} added and stirred until dissolved. With vigorous stirring, 2000 pounds (907.2 kg) of corn starch was added. Then, the required amount of 3% NaOH was added to the suspension at a rate of 4 lbs / min (1.8 kg / min) to obtain 40 ml of alkalinity (about 600 pounds (272.2 kg) of NaOH for 46 ml of alkalinity). The mixture was stirred for one hour and the pH was recorded (pH 11.6). The temperature was adjusted to 108 ° F (42 ° C). 200 pounds (90.7 kg) of 99/1 STMP / STPP was added and reaction continued for 17 hours. The final pH and temperature were recorded (pH 11.4 and 108 ° F (42 ° C)). The pH was adjusted to 5.5 using 3: 1 HCl (pH 5.4 after adding 75 pounds (34 kg) of HCl). The starch was washed, centrifuged in a Merco centrifuge and dried in a stream of hot air.

Samples 8, 9, 11, 13, 14, 15, and 16 were prepared using the same procedure as in the Sample 3 section. The 99/1 amount of the STMP / STPP mixture was adjusted to obtain the desired amount of bound phosphorus.

A sample of 18 - 750 ml of water was measured in the reaction vessel. While stirring, 2.5 g of NaCl was added and stirred until dissolved. To the saline was added 500 g of starch. The necessary amount of 3% NaOH was added dropwise to the suspension with vigorous stirring to obtain a pH of 11-11.5. The suspension was stirred for one hour and the pH was recorded (pH 11.43). 20 g of POCl ₃ was added and reaction continued for 30 minutes with stirring at room temperature. The pH was adjusted to 5.5 using 3: 1 HCl. The resulting starch precipitate was filtered and washed twice with 750 ml of tap water. The precipitate was crushed and dried in the open.

The amount of phosphorus bound and the amount of glucose released were determined for each of the raw starch samples. The results are presented below in table I.

Table I Starch base Sample No. STMP / STPP Bound phosphorus Glucose O / T (%) (% in starch) (%) 20 minutes 120 min 240 min Corn grain one Natural 0.04 17 75 85 Corn grain 2 8 0.12 17 71 80 Corn grain 3 8 0.21 9 48 62 Corn grain four 10 0.31 one 8 fifteen Corn grain 5 12 0.40 0 2 four

As follows from table I, sample 3 shows that starch can be crosslinked using a combination of STMP and STPP to change the digestion curve according to this invention. The digestion curves of such starches are presented in figure 2.

Example 2 - Isolation of glucose in food system models

Various basic starches modified STMP / STPP in accordance with the General procedure described in example 1, to obtain various total amounts of bound phosphorus. The digestibility of such starches as such or in food system models was determined.

The results are presented below in table II.

Sample No. Main starch Total amount of bound phosphorus (%) Model T = 20 min T = 120 min T = 240 min one Corn Absent. Absent. eighteen 80 85 2 Corn Absent. Biscuits 29th 73 80 3 Corn 0.24 Absent. one 27 60 four Corn 0.12 Biscuits 19 65 75 5 Corn 0.14 Biscuits fourteen 47 56 6 High (~ 70%) amylose content Absent. Absent. eleven 26 thirty 7 High (~ 70%) amylose content Absent. Biscuits 9 23 27 8 High (~ 70%) amylose content 0.23 Absent. 6 13 16 9 High (~ 70%) amylose content 0.25 Biscuits 7 16 eighteen 10 Tapioca Absent. Absent. 9 42 52 eleven Tapioca 0.15 Biscuits fourteen 46 58 12 Waxy corn Absent. Absent. 35 94 one hundred 13 Waxy corn 0.31 Biscuits 17 fifty 60 fourteen Waxy corn 0.41 Biscuits 12 31 36 fifteen Rice 0.17 Absent. 17 55 68 16 Wheat 0.21 Absent. 22 69 82

As follows from table II, various starch bases can be crosslinked using a combination of STMP and STPP to produce an altered digestion curve according to the invention in a food system model.

Example 3 - Comparison of Crosslinked Agents

The digestion of corn modified with STMP / STPP is compared with the digestion of corn modified with phosphorus oxychloride. The results are presented below in table III.

Table III Sample No. Sample Associated P (%) T = 20 (% GR) T = 120 (% GR) T = 240 (% GR) GRAIN STARCH one Corn grain Absent eighteen 80 90 17 Corn Grain STMP / STPP 0.26 one 27 58 eighteen Corn Grain POCl ₃ 0.27 0 2 2 COOKING MODEL 19 Corn Grain STMP / STPP 0.26 5 39 63 twenty Corn Grain POCl ₃ 0.27 3 eleven 16

As follows from table III, the product of corn grain as such or in the model for producing cookies does not give the digestion curves according to the present invention when modified with phosphorus oxychloride in the claimed range of bound phosphorus.

Example 4 - Food Products Containing Starch

Samples of starch from example 1 were added in an amount of 5-40% in order to replace flour or other carbohydrate ingredients in six different foods. All ingredients are presented in wt.% Of the total weight of the composition.

1) White molded bread

2) Semolina flour noodles

3) Nutrient tile

4) Flavored Drinking Yogurt

5) Tea biscuit

6) Products from grain crops

1) White molded bread

Patented flour 55.6 Granulated white sugar 4.3 Fat 2,8 Iodized salt 1,1 Active dry yeast 0.6 Conditioner for dough 35.0 Water 0.6 Total: 100.0

Cooking:

All ingredients and water were combined in a Hobart mixer. Stirred at low speed for 2 minutes. Stirred at medium speed for 14 minutes. Leave the dough for 5 minutes. Using the scales, the dough was divided into parts (510 g for 1/2 kg servings). Leave the dough for 5 minutes. Serves are shaped into a Glimek test dish. They were separated at 90% RH (relative humidity) and 80 ° C. Bake at 210 ° C for 22 minutes.

2) Semolina flour noodles

Semolina flour 74.1 Water 23.3 Dry egg whites 1,5 Conditioner for dough 1,1 Total: 100.0

Cooking:

All ingredients and water were combined in a Hobart mixer. Stirred at low speed for 10 minutes. Placed in a roll to get noodles. Cooked by placing the noodles in boiling water for 5-10 minutes with stirring. Drain the water.

3) Nutrition bar

Protein powder 33.6 Brown Rice Syrup 21.3 Dry oats 10.5 Honey 9.0 Skimmed milk powder 9.7 Soybean oil 2,8 Peanut flour 5.3 Apple Sauce or Raisin Paste 7.8 Total: one hundred

Cooking:

All dry ingredients (except oats) were combined in a Hobart mixer. Mixed at low speed for 5 minutes or until completely mixed. Stirring was continued by adding liquid ingredients. Oats were added while stirring at low speed. Tiles of the desired shape are molded by compression molding.

4) Flavored Drinking Yogurt

Whole milk up to 100.0 Sourdough (Danisco's Jo-mix 1-20) Skimmed milk powder not necessary Total: 100.0

Cooking yogurt:

Pre-heated milk to 65 ° C. Homogenized at 10.34 MPa, and then kept for 2 minutes at 93 ° C. The mixture was cooled to 44 ° C. Inoculated with leaven. Incubated to pH 4.5, and then cooled to 4.5 ° C. Yogurt could have the consistency of smooth cottage cheese.

Mix for juice:

Water 47.5 Strawberry Conc. (40-60 Brix) 40,0 Fructose 10.0 Pectin 2,5 Total: 100.0

Juice preparation:

Fructose and pectin were mixed in dry form. The dry mixture, water and strawberry concentrate were loaded into the mixer. Stirred until fructose and pectin were dispersed. The juice mixture was kept in a hot water bath at 80 ° C for 15 minutes. Cooled to 4.5 ° C.

Preparation of the finished product:

The yogurt and juice mixture were mixed in a 9: 1 ratio. Co-homogenized at 17.3 / 3.5 MPa (two stages). The finished product was stored at 4.5 ° C.

5) Tea biscuit

Wheat flour 48.0 Granulated white sugar 20.5 Whey powder 1.3 Baking powder 1,2 Salt 0.6 Fat 9.6 Egg yolks 2.0 Water 16.8 Total: 100.0

All dry ingredients and fat were combined in a Hobart mixer. Stirred at low speed for 5 minutes. Egg yolks and water were added. Stirred at low speed for 5 minutes. They molded or rolled out the dough and cut the biscuits. Baked at 176 ° C for 12-15 minutes.

6) Products from grain crops

a) Extruded grain product (based on maize)

Modified Maize Starch or Flour 40.0% Tortilla polenta 45.0% Sugar 10.0% Salt 2.0% Malt 3.0% 100.0% b) Extruded cereal product (multi-grain) Modified Maize Starch or Flour 43.0% Rice flour 11.5% Oat flour 11.5% Wheat flour 20.4% Sugar 9.0% Malt 2.6% Salt 2.0% 100.0%

Cooking:

Cereal products were prepared using methods known in the art. They were extruded, flakes were obtained and fried or extruded and expanded (expanded). Then, if necessary, the resulting product was dried to a final moisture content of less than 3%.

The resulting foods were digested using the Englist digestion method, and glucose release was determined after 20, 120 and 240 minutes. Glucose release was linear throughout the duration of digestion.

Claims (15)

1. A food product comprising crosslinked starch with added bound phosphorus in an amount of from 0.10 to 0.35%, said starch providing digestion of less than 25% of starch in 20 minutes, 30-70% in 120 minutes and more than 60% in 240 min when measured by the method of Englista, while the specified starch contains less than 40% amylose. 2. The product according to claim 1, in which starch provides less than 20% digestion of starch in 20 minutes 3. The product according to claim 1, in which starch provides less than 10% digestion of starch in 20 minutes 4. The product according to claim 1, in which starch provides 40-60% digestion of starch in 120 minutes 5. The product according to claim 1, in which starch provides 45-55% digestion of starch in 120 minutes 6. The product according to claim 1, in which starch provides more than 70% digestion of starch in 240 minutes 7. The product according to claim 1, in which starch provides more than 80% digestion of starch in 240 minutes 8. The product according to claim 1, in which starch provides more than 90% digestion of starch in 240 minutes 9. The product according to claim 1, in which the starch is crosslinked using a reagent selected from sodium trimetaphosphate, sodium tripolyphosphate, and combinations thereof. 10. The product according to claim 1, in which the starch is dextrinized. 11. The product according to claim 1, in which the starch is oxidized. 12. The product according to claim 1, in which starch is present in an amount of 5-40% based on dry weight. 13. The product according to claim 1, in which the rate of glucose release is essentially constant during the first 240 minutes 14. A method of regulating the glucose content in the blood of a mammal, comprising the consumption of a product according to claim 1. 15. A method of providing controlled delivery of glucose to a mammal, comprising consuming the product of claim 1.

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