KR101152167B1 - Functional nano starch complexes and their preparation methods - Google Patents

Abstract

The present invention relates to a method for preparing nano-sized particles by synthesizing a complex of starch or starch dextrin and various functional materials, and dissolving dextrin prepared from linear starch or starch in water or an aqueous solvent, an aqueous solution and Functional nanostarch complex, comprising mixing a hydrophobic functional material, enzymatically or acid treating the starch complex to remove non-compounded starch, washing and recovering the starch complex, and drying the recovered starch complex It relates to a manufacturing method.
According to the present invention, the nano-starch composite containing the functional material formed by the above method will have an effect of increasing the value of use as a product, such as accepting the insoluble material and improving stability as well as improving the bioabsorption rate. Therefore, it can be used in various fields such as food, medicine, cosmetics, chemical products as a carrier, coating agent and reinforcing agent of the functional material.

Description

Functional nano starch complexes and their preparation methods

The present invention relates to a method for preparing nano-sized particles by synthesizing a complex of starch or starch dextrin and various functional materials, and dissolving dextrin prepared from linear starch or starch in water or an aqueous solvent, an aqueous solution and Functional nanostarch complex, comprising mixing a hydrophobic functional material, enzymatically or acid treating the starch complex to remove non-compounded starch, washing and recovering the starch complex, and drying the recovered starch complex It relates to a manufacturing method.

Various functional ingredients such as hydrophobic or fat-soluble vitamins, omega 3 fatty acids, carotenoids, phytochemicals, antioxidants, food flavors, etc., are insoluble in water and are difficult to use in foods and cosmetics. It doesn't work well. As a method used to solubilize such an insoluble material, the conventional method was to use an emulsifier for each target material, but in general, a large amount of emulsifier used for emulsification is required, and thus, a unique taste and aroma of the target product are required. There is a problem that affects. In addition, some of the additives such as emulsifiers may be a problem for the stability of the human body, and the stability of the product is low because the emulsification power is reduced or altered during storage and distribution. In order to solve this problem, a technique for encapsulating functional food materials with carbohydrates such as cyclodextrin (CD) and cluster dextrin (CCD) has recently emerged. Since the inside of the CD and CCD molecules have a certain size of empty space and the outside is hydrophilic, the hydrophobic material can be enclosed inside and the solubility can be increased due to the hydrophilic outside. However, these materials have a disadvantage that the price is very expensive because they are obtained through a multi-step biological process of manufacturing and purifying with a specific enzyme or microorganism from starch. In addition, the materials that can be included are limited and the clathrates tend to form relatively large particles, making it difficult to produce nano-sized particles.

Starch is a cheap biopolymer obtained infinitely in nature as a storage of photosynthetic energy and is the main carbohydrate of food. Starch is not only used as an energy source for the human body but also used for food, cosmetics, and medicines as a role or additive to impart various functionalities. Starch is also used as a sustained release formulation that entraps and stabilizes various substances. Starches produced in plants are obtained in various forms of particles and have an average diameter of about 1 to 100 micrometers. Crystalline fine particles present in the granular starch can be used as a fat substitute because of its physical properties similar to fatty micelles, and can be applied as a filler to increase the strength of various materials including natural rubber [P. R. Kulkarni et al Carbohydrate polymer 53 (2003); R. L. Whistler et al. Cereal food world 35 (1990); A. Dufresne et al. Macromolecules 38 (2005)]. Small starch with reduced particle size is plasticized and crosslinking agent is added during processing to produce nanoparticles in polymer form [Y. Jiugao, L. Jie, Starch 46 (1994); Korean Patent Laid-Open No. 2001-0108128; It is reported that the preparation is possible by Korean Patent Laid-Open Publication 2001-0108052. According to the manufacturing method, starch particles having a size of 50 nm ~ 100 μm can be produced according to the manufacturing process and method, and are used for various applications such as pharmaceuticals, cosmetics, food, paints, coatings, papers and inks due to the fine particles. Can be. The method for preparing fine starch particles is added to the race chemicals such as emulsifiers and crosslinking agents and particles having no special functionality except particle size.

In addition to the above-mentioned manufacturing method, methods for preparing fine starch by enzyme or acid hydrolysis [A. Dufresne et al Macromolecules 38 (2005); Korean Unexamined Patent Publication No. 1995-0005843; Korean Patent Publication No. 10-0873015. According to this method, it is possible to produce fine particles composed of pure starch only by the hydrolysis process, but it is difficult to produce nano-level starch particles.

Accordingly, the present inventors have diligently researched to overcome the problems of the prior arts. As a result, when a nano-level complex containing a hydrophobic functional material is prepared using linear starch molecules or starch dextrins, simple nano-sized starches are prepared. It is confirmed that it is possible to accept and stabilize hydrophobic functional materials, not as particles, and also to produce such composites as nano-sized small sized particles to improve bioavailability and increase functionality in various fields. The present invention has been completed.

Therefore, the main object of the present invention is to increase the bioabsorption rate and the hydrophobic functionality by using starch or starch dextrin which is harmless to the human body and does not affect the flavor and taste of the product as it is tasteless, odorless, and colorless substance and is highly applicable to various products. The present invention provides a functional nanostarch composite having a merit of increasing the water solubility and stability of a material, and a method for preparing the same.

According to an aspect of the present invention, the present invention provides a method for preparing a nanostarch composite, comprising the following steps:

a) dissolving linear starch or dextrin in an aqueous solvent;

b) mixing the aqueous solution with a hydrophobic functional material;

c) enzyme or acid treatment of the product of step b);

d) washing and recovering the result of step c);

e) drying the recovered starch complex.

The starch of the present invention is a linear starch chain in which glucose is polymerized linearly by α (1-4) linkage, preferably linear amylose or linear dextrin is alcohol, fatty acid, emulsifier, vitamin, flavor component such as various hydrophobic molecules It can form a complex with. Such a composite has a form in which linear starch chains spirally surround a guest compound as shown in the schematic diagram of FIG. 1. As shown in the schematic diagram of FIG. 1, such a spiral complex forms a crystalline structure in a constant arrangement, and the shape of the crystal varies somewhat depending on the production conditions. The size of these crystals depends on complex formation conditions, but reports have been reported to be approximately 2-12 μm in diameter [J. Brisson et al., International Journal of Biological Macromolecules 12 (1990); M. A. Whittam et al., International Journal of Biological Macromolecules 11 (1989)]. In the present invention, it is a technology that allows starch chains to naturally form a complex with a clathrate by self-assembly by distributing such a spiral complex to disperse in an aqueous solution. To this end, it is important to suppress aggregation between starch chains to the maximum and to induce a maximum reaction between clathrate and starch.

In the method of preparing a nanostarch composite of the present invention, the starch of step a) may be used as any starch which may form a complex with alcohol, but preferably, general corn starch, high amylose corn starch, waxy corn starch, rice starch. , Starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch, starch , Starch selected from the group consisting of sorghum starch, waxy starch, banana starch, mung bean starch, eastern starch, kuzukiri starch, derivatives of these starches and amylose extracted from these starches. In order to prove that the nanostarch complex can be prepared from all of the above, high amylose corn starch was used in Examples 1, 2 and 4 and nanostarch was used in Example 3 using waxy corn starch. The complex was prepared.

In the nanostarch composite production method of the present invention, the dextrin of step a) is characterized in that the prepared by converting the starch by dextrinization. The dextrinization is 1-6 binding to alpha amylase (α-amylase), beta amylase (β-amylase), glucoamylase, amyloglucosidase, alpha glucosidase (α-glucosidase) It is preferable to use any one starch degrading enzyme or a mixed enzyme thereof selected from the group consisting of hydrolysable isoamylase and pullulanase. In addition, the dextrinization may be performed using any one selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and organic acids such as acetic acid, citric acid, malic acid, or mixtures thereof.

In the method of preparing a nanostarch composite of the present invention, the starch or dextrin concentration of step a) may be used in a concentration of 0.01 to 20.0%, preferably 0.1 to 5.0%. Dextrins having a low molecular weight have no problem even if the concentration is somewhat high, but if the concentration is too high, aggregation between starch or dextrin molecules may occur, and thus complex formation is not easy.

In the nanostarch composite manufacturing method of the present invention, the hydrophobic functional material used in the step b) is hydrophobic so that only a spiral structure can be included by forming a complex of linear starch or dextrin molecule and V-type, and the human body. Or any conventionally known substance having useful functionality to the organism, but preferably in the carotenoid substance, antheraxanthin, astaxanthin, alpha-carotene, beta-carotene, and beta-carotene. carotene, beta-apo-4'-carotenal, beta-apo-8'-carotenal, canthaxanthin Citraaxanthin, cryptoxanthin, dehydroplectaniaxanthin, diatoxanthin, fucoxanthin, fucoxanthinol, lactucaxin , Lutei n), lycopene, neoxanthin, neurorosporaxanthin, neurorosporene, peridinin, phytoene, rhodopin, siponoxanthin (siphonaxanthin), spheroidene, spirilloxanthin, toruloladin (torularodin), uriolide, uriolide acetate, violaxanthin, zeolaxanthin (zeaxanthin), nerol, nerolidol, citral, cinamaldehyde, citronellol, cis-3-hexenal, vanillin in fragrances vanillin, isoamyl acetate, 1-octen-3-one, octyl acetate, cadaverine, hexanal, masoiarac Massoia lactone, menthol, methyl butyrate, menthone, pentyl butyrate, pentylphene Pentyl pentanoate, linalool, geraniol, decanal, 1-naphthol and other nutrients, fish oil, beeswax, D Fat-soluble vitamins such as D-limonene, and vitamin A, vitamin E, and coenzyme Q-ten (Co-Q10) (cokyuten) and vitamin-like substances, fatty acids such as lecithin, DHA, EPA, flavors such as capsaicin, and hydrophobicity Preference is given to those selected from the group consisting of drug components. In the embodiment of the present invention, as an example of the functional material, the experiment was carried out to form a complex by inclusion of beta carotene and cocuten on the nano deck screen, but other hydrophobic functional materials other than the inclusion material is naturally also included in the nano dextrin It will be apparent to those skilled in the art that the complex can be formed.

In the method for preparing a nanostarch composite of the present invention, the step b) is characterized in that it comprises the steps of b-1) dissolving a hydrophobic functional material in a hydrophobic solvent and b-2) mixing the hydrophobic solution and an aqueous solution. .

In the nanostarch composite manufacturing method of the present invention, the step of mixing the hydrophobic solution and the aqueous solution of step b-2) is characterized in that the method for forming a starch complex using a phase separation phenomenon. Generally, starch molecules and clathrates are directly mixed to synthesize a complex. In this case, the yield of complex formation is low and large particles are formed because crystals are likely to grow largely or form amorphous precipitates. However, in the phase-separated system as shown in FIG. 2, the reaction between the two molecules is controlled because the functional material dissolved in the hydrophobic solvent and the starch molecules of the aqueous solution may be in physical contact only at the boundary where the phase separation takes place. Thus, suitable conditions for forming the complex are formed and are produced as nano-sized particles. This particle has a structure that wraps the functional material inside the starch molecule, so that the hydrophobic functional material can be water-soluble, and by blocking the external environment, it inhibits oxidation and enzymatic reactions, thereby preventing the phenomenon of being stable and easily released. Therefore, it is effective in maintaining the functionality and activity of the encapsulated material for a long time. In addition, since the particle size is reduced to the nano-area will be able to be effectively applied in a variety of fields.

In an embodiment of the present invention, the phase separation was performed by slowly injecting a hydrophobic solution onto the aqueous solution so that phase separation was achieved without breaking the interface between the two solutions. In the embodiment of the present invention, the amount of the hydrophobic solution is injected in half of the amount of the aqueous solution, but a smaller amount may be used or a larger amount may be used.

In the nanostarch composite manufacturing method of the present invention, the hydrophobic solvent of the step b-1) is that the component does not form a complex with the starch or lower than the complex forming ability of the functional material, all the phase separation with water Hydrophobic solvents can be used. The hydrophobic solvent is hexane, cyclohexane, isopropyl ether (iso-propyl ether), decalin (decalin), methyl tert-butyl ether (methly tert-butyl ether (MTBE), ethyl ether, petroleum ether ( petroleum ether), preferably selected from the group consisting of vegetable oils.

In the nanostarch composite manufacturing method of the present invention, it provides a nanostarch composite manufacturing method comprising the step of mixing the functional material of the step b) directly to starch or dextrin aqueous solution without dissolving in a hydrophobic solvent. As mentioned above, when the composite is synthesized by directly mixing the clathrate in an aqueous solution of starch or dextrin, the nanoparticles are formed, but the composite particles may grow because crystals may grow large. In order to solve the above problems, the present inventors maintain the above production method and utilize starch dextrin having a low molecular weight thereto, and also increase the mixing and stirring speed to prepare a smaller size of the composite.

In the nanostarch composite production method of the present invention, the step of forming a complex of the starch or dextrin solution and hydrophobic solution of step b) is preferably carried out at a temperature of 10 ℃ to 100 ℃. When the reaction is carried out at a temperature lower than the above range, the mobility of starch molecules is lowered and the solubility of starch is lowered to cause aggregation between starch molecules. When the reaction is carried out at a temperature higher than the above range, it may cause evaporation of the reaction solvent and the starch complex formed may be melted again. In the embodiment of the present invention was carried out at a reaction temperature of 50 ℃, in this case is the most preferred because it is easy to form a complex with sufficient mobility of starch molecules, and can suppress evaporation of the solvent.

In the nanostarch composite production method of the present invention, the step of removing the starch molecules that do not participate in the complex formation of step c) includes a process by starch dehydrogenase or an acid solution. In the food processing field, all starch enzymes commonly used for processing raw starch particles from corn, potatoes, rice, wheat, etc. may be used, and preferably alpha amylases capable of hydrolyzing 1-4 bonds in starch molecules. (Iso-amylase), beta amylase (β-amylase), glucoamylase, amyloglucosidase, and isoglucosidase (α-glucosidase) to hydrolyze 1-6 bonds Amylase (iso-amylase), pullulanase (pullulanase) is selected from the group consisting of.

In the nanostarch composite production method of the present invention, the starch molecule removal step of step c) can be hydrolyzed using any acid solution in addition to starch degrading enzyme. The acid used for acid hydrolysis may be any acid commonly used in the food processing field, preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, or acetic acid. Initial use of dextrin can reduce the amount of enzyme and acid used since most dextrin molecules can be involved in complex formation, or the process can be omitted. The starch molecules decomposed by the enzyme and acid remain in a dissolved state in an aqueous solution and are subsequently removed in the washing process.

In the nanostarch composite manufacturing method of the present invention, the washing of the complex in the washing and recovery process of step d) minimizes the structural change, and it is preferable to use a solvent of alcohols in which the entrapped material is not removed from the complex. When the starch complex precipitates, it can be recovered by simple filtration and centrifugation.

In the method of manufacturing a nanostarch composite of the present invention, the recovered starch complex of step e) may be dried using various drying methods such as vacuum drying, freeze drying, investment drying, hot air drying, and spray drying. The starch composite is in a solid powder state by the drying process.

In the nanostarch composite production method of the present invention, the obtained composite aqueous solution can be utilized directly in the product without undergoing the washing and recovery process of the production method e) step.

The complex of the starch or dextrin and the functional material of the present invention forms a nanoparticle by forming a structure surrounded by a spiral of functional molecules in a linear portion in which 5 to 10 glucoses are bonded by α (1-4) bonds. do. In addition, in the complex, the functional material may exist between the helical units depending on the type of the functional material. The complex has nano-sized particles, and since the helical structure of these particles is hydrophilic on the outside while hydrophobic on the inside, various hydrophobic functional materials can be included in the helical structure, and the entrapped material is made of water by the helical outer structure which is hydrophilic. Easily soluble in Therefore, the various hydrophobic functional materials can be easily accommodated, so that the hydrophobic functional food material or drug component can be delivered more efficiently, and these substances can be prevented from being oxidized or denatured along the way. In addition, hydrophobic flavor components can be enclosed within the helical structure, and these components can be prevented from easily volatilizing, thereby making it possible to store and deliver more stably. Therefore, the nano starch complex may be used to capture and deliver functional substances or pharmaceutical ingredients in the food, cosmetic, or pharmaceutical industries.

According to another aspect of the present invention, the present invention provides a nano starch composite prepared by the preparation method according to the above method. Nano-sized fine starch particles of the present invention can be used in a variety of applications in the textile, paper, chemical industry and food industry. Specifically, in the food industry, it can be used as a dispersing agent, a flavor preservative, etc. in the food industry, and in the textile industry, it can be used as protection of yarn, printing, and coating for improving the weaving of fiber yarns, and in the paper industry, surface sizing agents and coating agents. It can be used as an internal additive and an interlayer adhesive of cardboard. In the chemical industry, starch may be denatured and used as a powder such as an adhesive, a dispersant, and an anti-slip agent. In addition, it can be used as a filler to improve physical properties by adding to plastic films, molded products, and the like, and can also be used as a raw material for various absorbent resins.

1 is a diagram illustrating a complex formation process in which linear starch or dextrin is incorporated with a functional material.
2 is a view showing a method for producing nanostarch particles using phase separation.
Figure 3 is a view showing the change in the concentration of beta carotene in the upper layer when preparing the nano dextrin-beta carotene complex.
Figure 4 is a view showing the form of the nano dextrin-beta carotene complex.
5 is a graph showing particle size distribution of nanodextrin-beta carotene complex.
6 is a diagram showing an X-ray diffraction diagram of the nanodextrin-beta carotene complex.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and the scope of the present invention is not to be construed as being limited by these examples.

Example  1. Preparation of Nano Dextrin-Beta Carotene Complex

1) Dextrin Manufacturing

25 g of high amylose corn starch (Hylon VII, amylose content 70%, National starch, Bridgewater, NI, USA) was dispersed in 100 mL of 100% ethanol, and then 1 mL of 36% HCl was added and stirred well. The mixed suspension was reacted at 20 ° C. for 72 hours and then washed with 50% ethanol until all acid and hydrolyzed sugars were removed. After washing once with acetone, it was dried for 12 hours at 40 ℃ and then ground.

2) Dextrin-beta carotene complex synthesis

1 g of dextrin was dispersed in 100 mL of distilled water, and then heated at 131 ° C. for 20 minutes to dissolve dextrin. 10 mg of beta-carotene was dissolved in 50 mL of isopropyl ether, and the isopropyl ether solution was slowly added to the dextrin solution to cause phase separation from the dextrin solution as shown in FIG. 2. The dextrin solution was then reacted at 50 ° C. for 72 hours with stirring at 150 rpm.

3) Recovery of dextrin-beta carotene complex

After 72 hours, the aqueous solution containing the complex was precipitated by high speed centrifugation (× 20,000 g ) and recovered. The reason for using isopropyl ether as a solvent of beta carotene in this embodiment is that isopropyl ether is a solvent in which beta carotene is dissolved well and phase separation with water does not form a complex with starch.

Test Example  1. Dextrin-beta carotene complex formation Supernatant  Beta Carotene Content

Absorbance at 448 nm using a UV-Visible Spectrophotometer (Ultrospec 2000 UV / Visible Spectrophotometer, Pharmacia Biotech, UK) to change the beta carotene content of the upper layer during the crystallization process of the nanodextrin-beta carotene particles prepared in Example 1 It was measured by the change of. As shown in Figure 3 beta carotene content decreased over time. This phenomenon can be seen that the beta carotene content of the upper layer is reduced as the beta carotene molecule of the upper layer complexes with the dextrin molecule of the lower layer. The slight increase in beta-carotene content after 2 days of reaction can be seen as the content increased as a small amount of isopropyl ether (boiling point: 68.27 ℃) during the reaction.

Test Example  2. Morphological Changes of Nanodextrin-beta-carotene Particles

The crystallinity, particle size, particle shape, etc. of the nanodextrin-beta carotene particles prepared in Example 1 were measured. Morphological changes of the dextrin-beta-carotene complex were observed using a transmission electron microscope (Philips Tecnai 12, Netherlands). The complex was observed after staining with uranyl acetate. As shown in FIG. 4, the dextrin-beta carotene complex is a nano-level particle having a polygonal shape of 50 to 300 nm.

Test Example  3. Observation of nanoscale particle size and distribution

The average diameter and particle size distribution of the dextrin-beta carotene particles prepared in Example 1 were measured using a particle analyzer (Dynapro Titan, Wyatt Technology, SantaBarbara, CA). As shown in FIG. 5, the nano-level starch particles had a size of about 100-300 nm with about 80% of the particles and about 20% of the particles having an average particle size of the micro level. These results indicate that approximately 80% of the particles are nanoscale particles, but 20% of the particles aggregate together to form a micro sized mass. Therefore, in the present embodiment, the dextrin-beta-carotene composite particles having a size of most of the particles were prepared.

Test Example  4. Nano-level particle crystalline

The crystallinity of the dextrin-beta carotene complex was measured using an X-ray diffraction analyzer (MO3XHF22 MAC science CO. Japan). It was measured from 3 ° to 30 ° at a rate of 1.0 ° / min at 40 kV, 40 mA conditions. As shown in Figure 6, in the case of the dextrin-beta-carotene complex, two peaks can be observed in the analysis result graph, both peaks of the V6-I crystal form. Crystals in the V6-I form are crystalline when amylose and fats and alcohols form spiral complexes. The helical crystal is twisted around the entrapped molecule, and has a structure in which six glucose units are consumed and the space inside the helical crystal is reported to be 0.805 nm [Rappenecker G. et al., Carbohydrate Research 89 (1981); Bul? On A. et al., Carbohydrate Polymers 4 (1984)]. Therefore, it can be confirmed that beta carotene is contained in the spiral crystal.

Example  2. Preparation of Nano Starch-beta-carotene Complex

1) Starch-beta carotene complex synthesis

1 g of high amylose corn starch was dispersed in 100 mL of distilled water and heated at 121 ° C. for 20 minutes to dissolve it. After dissolving 10 mg of beta carotene in 50 mL of isopropyl ether, the isopropyl ether solution was slowly added to the starch solution to cause phase separation as shown in FIG. 3. The starch solution was then reacted at 50 ° C. for 72 hours with stirring at 150 rpm.

2) recovery of starch-beta carotene complex

After 72 hours, the upper layer was removed using a pipette, and only the starch solution containing the complex of the lower layer was separated, and alpha amylase (500 unit) was added to the solution and stirred at 50 ° C. for 1 hour. In this process, starch chains that do not form complexes are broken down, leaving only the complexes. The starch complex was then precipitated and recovered by high speed centrifugation (× 20,000 g ).

Test Example  1. Observation of Particle Size, Distribution and Crystallinity of Nano Starch-Betacarotin

The particle size distribution was measured for the average diameter of the composite prepared in Example 2 using a particle analyzer. The composite dispersed in the aqueous solution before centrifugation was distributed as starch particles having an average particle size of 100 ~ 200 nm. In addition, the crystallinity was measured using an X-ray diffractometer and showed V6-I crystallinity.

Example  3. Nano Waxy Dextrin- Kokyuten  Manufacture of Composites

1) Dextrin Manufacturing

After dissolving 1 g of starch corn starch in 99 mL of distilled water, acetate buffer solution (1M, pH 3.5, 1 mL) was added, and 30,000 units of isoamylase were added and hydrolyzed at 45 ° C. for 24 hours. After completion of the hydrolysis reaction, the pH was adjusted to 6.5, and then the enzyme was inactivated in boiling water for 10 minutes to terminate the reaction.

2) Synthesis of Dextrin-Cocuten Complex

3 g of the prepared dextrin was dispersed in 100 mL of distilled water, and then dissolved by heating at 121 ° C. for 20 minutes. 100 mg of CoQ10 was added to the dextrin solution and reacted at 50 ° C. for 72 hours while stirring at 150 rpm. During this process, cocuten forms a complex with dextrin and is evenly distributed in the aqueous solution.

3) Recovery of Dextrin-Cocuten Complex

After 72 hours reaction, the aqueous solution containing the complex was centrifuged at high speed (x20,000 g ) and recovered. The content of cocutene in the recovered complex was about 60-80 mg and it was confirmed that 60% or more of cocuten added with dextrin was reacted.

Test Example  1. Dextrin Kokyuten  Observation of particle size, distribution and crystallinity

Using a particle analyzer, the average diameter and particle size distribution of the composite prepared in Example 3 were measured. The dextrin-coutene complex dispersed in the solution was distributed into starch particles having an average particle size of 60-100 nm. In addition, the crystallinity of the dextrin-cocuten complex was measured using an X-ray diffractometer.

Example  4. Nano Corn Dextrin- Kokyuten  Manufacture of Composites

1) dextrin manufacturer

25 g of high amylose corn starch was dispersed in 100 mL of 100% ethanol, and then 1 mL of 36% HCl was added, followed by stirring well. The mixed suspension was reacted at 20 ° C. for 72 hours and then washed with 50% ethanol until all acid and hydrolyzed sugars were removed. After washing once with acetone, it was dried for 12 hours at 40 ℃ and then ground.

2) Synthesis of Dextrin-Cocuten Complex

3 g of the prepared dextrin was dispersed in 100 mL of distilled water, and then dissolved by heating at 121 ° C. for 20 minutes. 1 g of CoQ10 was added to the dextrin solution and reacted at 50 ° C. for 72 hours while stirring at 150 rpm. During this process, cocuten forms a complex with dextrin and is evenly distributed in the aqueous solution.

3) Recovery of Dextrin-Cocuten Complex

After 72 hours, the aqueous solution containing the complex was precipitated and recovered by high speed centrifugation (× 20,000 g ). Cocutene content of the recovered complex was confirmed that more than 90% of the cocuten added to about 80 ~ 90 mg reacted with dextrin.

Test Example  1. Observation of particle size and crystallinity

The particle size distribution was measured for the average diameter of the composite prepared in Example 4 using a particle analyzer. The dextrin-cocutene complex dispersed in the solution was distributed into starch particles having an average particle size of 80 to 200 nm. In addition, the crystallinity of the dextrin-cocuten complex was measured using an X-ray diffractometer.

As mentioned above, according to the present invention, nano-level particles can be prepared by forming starch and starch dextrin in complex with inclusion materials of various hydrophobic materials. The prepared nano starch particles accept the encapsulated hydrophobic material and convert it for use in various products. In addition, it is expected that the composite may be formed to nanoparticle size to increase the bioabsorption rate and increase the stability of the inclusion material. Therefore, such nanoparticles can be usefully applied as a functional material or a drug delivery material in the food, cosmetics and pharmaceutical industries. In addition, it is expected to be used in a variety of industries, such as fat replacement, coatings, capsules, reinforcing agents.

Claims (13)

Method for producing a nanostarch composite containing a functional material comprising the following steps:
a) dissolving linear starch or dextrin polymerized linearly by α (1-4) bond in distilled water;
b) mixing the starch or dextrin aqueous solution with the carotenoid hydrophobic material;
c) treating the resultant of step b) with a starch enzyme or acid;
d) washing and recovering the result of step c); And
e) drying the recovered starch complex,
Starch of step a) is a general corn starch, high amylose corn starch, waxy corn starch, rice starch, glutinous rice starch, high amylose rice starch, potato starch, waxy potato starch, sweet potato starch, barley starch, waxy barley starch, soybean ( pea starch, wheat starch, waxy starch, sago starch, amaranth starch, tapioca starch, sorghum starch, brisket starch, banana starch, mung bean starch, eastern starch, kuzukiri starch, these starch Derivatives, and amylose extracted from these starches,
The carotenoid hydrophobic material of step b) is characterized in that beta carotene or coenzyme Q10 (Co-Q10).
delete The method of claim 1, wherein the dextrin of step a) is a method for producing a nanostarch complex, characterized in that the conversion by dextrinization of starch.
The dextrinization of claim 3, wherein the dextrinization is capable of hydrolyzing 1-4 bonds (α-amylase), beta amylase (β-amylase), glucoamylase, amyloglucosidase (amyloglucosidase). ), An isoamylase capable of hydrolyzing 1-6 bonds with alpha-glucosidase, and a starch degrading enzyme selected from the group consisting of pullulanase or mixed Nanostarch composite production method characterized in that dextrinization of starch using an enzyme.
The dextrinization of the starch is characterized in that the starch is dextrinized using any one acid or mixture selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and organic acid, acetic acid, citric acid and malic acid. Nano starch composite production method.
The method of claim 1, wherein the starch or dextrin concentration of step a) is a method for producing a nanostarch composite, characterized in that using a starch or dextrin concentration of 0.01% to 20.0%.
delete delete The method of claim 1, wherein the forming step of the complex of starch and dextrin and the functional material of step b) is carried out at a reaction temperature of 10 ℃ to 100 ℃.
According to claim 1, wherein in step c) can be hydrolyzed 1-6 bonds with alpha amylase, beta amylase, glucoamylase, amyloglucosidase, alphaglucosidase, which can hydrolyze 1-4 bonds. Method for producing a nanostarch complex, characterized in that by using any one or mixed starch degrading enzyme selected from the group consisting of isoamylase and flulanase to decompose starch not involved in complex formation.
The method of claim 1, wherein in step c), an aqueous solution of any one acid or mixture selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and organic acids, such as inorganic acid, acetic acid, citric acid, and malic acid, is not used in the formation of the complex. Nanostarch composite manufacturing method characterized by decomposing starch.
The method of claim 1, wherein the drying step e) comprises drying by vacuum drying, freeze drying, investment drying, hot air drying or spray drying.
A nanostarch composite prepared by the method according to any one of claims 1, 3 to 6, and 9 to 12.

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