WO2011004944A1 - Nano composite formed from starch and functional materials, and method for preparing same - Google Patents

Abstract

The present invention relates to a method for preparing a nano particle by synthesizing a composite of starch or dextrin and various functional materials. The method comprises the steps of: dissolving starch or dextrin prepared from starch into water or a water-soluble solvent; dissolving functional materials to be included into a hydrophobic solvent; adding the hydrophobic solvent into the aqueous starch solution and agitating the result; forming a starch composite; eliminating residual starch; and collecting the starch composite, wherein some of the functional materials can be added directly to the aqueous starch solution, rather than be dissolved into the aqueous solution, thereby forming the starch composite. During the process of forming the composite, aggregation of starch or dextrin should be suppressed and the reaction rate needs to be controlled for including functional materials. The nano starch composite, which includes the functional materials, allows insoluble materials to be soluble and increases stability and in-vivo absorption, and is thus expected to have the effect of increasing the usefulness as products. Therefore, the nano starch composite can be used as a carrier, a coating agent, and a reinforcing agent for functional materials in various fields, such as fields of food, medicine, cosmetics, and chemical products.

Description

Nano-sized composites combining starch and functional materials and preparation method thereof

The present invention relates to a nano-sized composite in which starch and a functional material are combined, and a method for preparing the same. More particularly, the present invention relates to a starch or starch dextrin, which includes a hydrophobic functional material to form a helical complex to accommodate a hydrophobic functional material. The present invention relates to a method for producing stabilized nano starch particles and a composite produced by the method.

In general, various functional ingredients such as hydrophobic or fat-soluble vitamins, omega 3 fatty acids, carotenoids, or food flavoring ingredients used in foods, cosmetics, and medicines are insoluble in water, making them difficult to use in foods, cosmetics, etc. Absorption does not work well even when applied. In order to overcome this, it can be solubilized by the preparation of emulsions, liposomes, etc., but additives such as some emulsifiers may be a problem for human safety, and the stability of the product is low during storage and distribution. In addition, there is a problem that these additives adversely affect the flavor (flavor) and taste (taste) to affect the taste and aroma of the target product inherent.

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 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 biological process prepared and purified by using a specific enzyme or microorganism from starch. In addition, the CD clathrate obtained in the aqueous solution is difficult to manufacture the nano-sized particles because it has the property of forming large particles as a whole when the concentration is high. Yifeng He et al. Micron 39 (2008).             

Starch, on the other hand, is a cheap carbohydrate polymer obtained infinitely in nature as a storage material for photosynthetic energy and is a major carbohydrate in food. Starch is used not only as an energy source but also as a additive to foods, cosmetics and medicines. Starch may also be used as a sustained release formulation that entraps and stabilizes various substances. Starches produced in plants are obtained in various forms of particles, with an average diameter of about 1-100 micrometers. Crystalline fine particles present in the granular starch can be used as a fat replacement agent because it has 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. By using the manufacturing method, it is possible to produce starch particles having a size of 50 nm-100 μm according to the manufacturing process and method, and because of the fine particles, they can be used in various applications such as medicine, cosmetics, food, paint, coating, paper and ink. Can be. The method for preparing fine starch particles is added to artificial chemicals such as emulsifiers and crosslinking agents and are particles having no special functionality except particle size.

In addition to the production method specified above, 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 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.

It is an object of the present invention to provide a method for preparing a composite of nanoparticles containing a hydrophobic functional material by using starch or starch dextrin.

Another object of the present invention is to provide a composite of nanoparticles containing a hydrophobic functional material prepared by the above method.

In order to achieve the above object, the present invention provides a method for preparing a polymer comprising: a) dissolving linear starch or dextrin in a water-soluble solvent; b) dissolving a functional material in a hydrophobic solvent; c) the hydrophobic solution and the starch comprising a functional material. Or mixing dextrin aqueous solution; And d) a nano-sized combination of starch and a functional material in a V-amylose form (starch molecule spirally wrapped in a functional material), comprising the step of changing the structure by enzymatic or acid treatment of the resultant of step c). It provides a method for producing a composite.

In one embodiment of the present invention, the linear starch or dextrin of step a) means that the starch molecule is degraded by acid, enzyme, micro ray irradiation, or radiation irradiation, and is preferably converted by dextrinization. It is not limited.

'Nano size' in the present invention is the broadest meaning commonly used in the art, preferably 10 to 500nm is not limited thereto.

In one embodiment of the present invention, the linear starch or dextrin of step a) is preferably converted by dextrinization of starch, but is not limited thereto.

The starch of the present invention is a linear starch chain in which glucose is polymerized linearly by α (1-4) bond, preferably linear amylose or linear dextrin is complexed with various hydrophobic molecules such as fatty acids, emulsifiers, vitamins, flavor components, etc. Can be formed. 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.

The manufacturing method 1 of this invention by this invention is demonstrated.

In this method, a starch complex different from the conventional one was synthesized by using a phase separation phenomenon of a water-soluble solvent and a hydrophobic solvent. Generally, starch molecules and clathrates are directly mixed to synthesize a complex. In this case, the yield of complex formation is low and large grains 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 clathrate and the starch molecules of the water-soluble solvent dissolved in the hydrophobic solvent may be in physical contact only at the boundary where the phase separation takes place, thereby controlling the reaction between the two molecules. Thus, suitable conditions for forming the complex are formed and are produced as nano-sized particles. The particles have a structure that surrounds the inclusion material inside the starch molecule, so that the hydrophobic inclusion material can be water-soluble, and by blocking the external environment, it inhibits oxidation and enzymatic reactions, thereby preventing stable and easily released phenomena. 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, it can be effectively applied in various fields.

In the method for preparing nanostarch particles of the present invention, the starch of step a) may be used any starch that can form a complex with the inclusion material, ordinary corn starch, high amylose corn starch, waxy corn starch, rice starch, glutinous rice Starch, goamylose rice starch, potato starch, potato potato starch, sweet potato starch, barley starch, waxy barley starch, soybean starch, wheat starch, waxy starch, sago starch, amaranth starch, tapioca starch, sorghum ), Starch, starch starch, banana starch, mung bean starch, eastern starch, kuzukiri starch, derivatives of these starches, dextrins of these starches, and starches selected from the group consisting of amylose extracted from these starches. In the present invention, the derivative of starch includes substituted starch, crosslinked starch, oxidized starch, etc., which artificially changed the structure of starch, and dextrin of starch is natural starch enzyme or acid treatment, heating and micro ray and irradiation, etc. By means of the decomposition means a low molecular weight product, the amylose extracted from these starch means a relatively linear starch molecule extracted by hot water extraction or alcohol extraction from natural starch.

In the method for preparing nanostarch particles of the present invention, it is preferable to use a starch or dextrin solution having a concentration of 10.0% or less in the step a). Dextrins having a low molecular weight are not a problem even if the concentration is slightly higher, but at higher concentrations, it is not preferable because the formation of complexes with clathrates may be delayed due to aggregation between starch or dextrin molecules.

In the method for preparing nanostarch particles of the present invention, the hydrophobic solvent used in the steps b) and c) preferably does not form a complex with starch or has a lower complexing capacity than the inclusion material, and phase separation occurs with water. Any hydrophobic solvent can be used. The hexane, cyclohexane, iso-propyl ether, decalin, methyl tert- butyl ether, ethyl ether, petroleum ether, vegetable oils are suitable for this.

The clathrate can be any substance which can form a complex with the starch chain. Ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and alcohols and isomers, beta-carotene Carotenoids such as retinol, fat-soluble vitamins such as vitamin A, vitamin E, coQ10, fatty acids such as lecithin, DHA, EPA, flavors such as menthone, linalool, graniol, decanal, 1-paphtol, capsaicin, and hydrophobic drugs Preference is given to those selected from the group consisting of components.

In the method of preparing nanostarch particles of the present invention, the reaction temperature in step c) is preferably 10-100 ° C. This is because, at 10 ° C. or less, starch mobility decreases and solubility of starch decreases, so that aggregation between starch molecules is likely to occur. Above 100 ° C, the reaction solvent may be easily volatilized and is not preferable because the formed starch complex may be melted again.

In step d) of the method for preparing nanostarch particles of the present invention, a step of removing starch molecules that do not participate in complex formation includes a process by enzyme and acid treatment. Starch degrading enzymes are all starch degrading enzymes commonly used to process raw starch particles from corn, potatoes, rice, wheat, etc. in the food processing field, and alpha amylases that can hydrolyze 1-4 bonds in starch molecules. , Beta amylase, glucoamylase, alpha-glucosidase and isoamylase capable of hydrolyzing 1-6 bonds and those selected from the group consisting of pullulase. Acid used for acid hydrolysis may be any acid commonly used in food processing, and is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and acetic acid. Initial use of dextrin can reduce the amount of enzymes and acids used since most of the dextrin molecules can be involved in complex formation, and this process can be omitted. The decomposed starch molecules remain dissolved in the aqueous solution and can be removed later in the washing process. In this case, a method of inducing annealing by preserving at a constant temperature for a long time may be utilized. In other words, starch molecules that do not participate in complex formation may bind to each other to help the composite particles remain stable in a small state. This physical treatment temperature is suitably between 10 and 100 ° C. at which the composite does not decompose.

After the step d) in the method for preparing nanostarch particles of the present invention, the complex may be separated by washing and recovery. The washing of the complex minimizes structural changes and preferably uses a solvent of alcohols in which the entrapped material is not removed from the complex, whereby the starch complex is precipitated and can be recovered by simple filtration and centrifugation. The recovered starch composite may be dried and recovered as a powder product using various drying methods such as vacuum drying, freeze drying, investment drying, hot air drying and spray drying. The composite aqueous solution obtained in step c) and d) of the present invention may be directly used in a product without undergoing washing and recovery.

The manufacturing method 2 according to the present invention will be described.

As mentioned above, the composite is synthesized by directly mixing the clathrate with an aqueous solution of starch or dextrin, and in this case, since the crystals are likely to grow significantly, the composite particles are usually large. However, in the production method 2 of the present invention, in order to solve such a problem, it is preferable to utilize the starch dextrin having a low molecular weight or to increase the mixing and stirring speed to make the size of the composite smaller.

Except for directly mixing the inclusion material without using a hydrophobic solvent in the a) process of the method for preparing nanostarch particles of the present invention, other processes may be applied in the same manner as in the preparation method 1.

In one embodiment of the present invention, the dextrinization may be used for all starch enzymes commonly used to process raw starch particles from corn, potatoes, rice, wheat, etc. in the food processing field, for example, 1 Α-amylase, glucoamylase, α-glucosidase, β-amylase capable of breaking down glycosidic bonds, and iso-amylase and pullula, which can hydrolyze 1-6 glycosidic bonds Dextrinization of starch using any one starch degrading enzyme selected from the group consisting of Naase or a mixture of the above enzymes is not limited thereto.

In another embodiment of the present invention, the dextrinization is used for all acids commonly used in the food processing field, for example any one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, malic acid and acetic acid It is preferred, but not limited to, to dextrinize starch using an acid or a mixture of acids.

In another embodiment of the present invention, the dextrinization is preferably, but not limited to, dextrinization of starch by using microrays or irradiation commonly used in the food processing field.

In one embodiment of the present invention, the concentration of the starch or dextrin used in step a) is not a problem even if the concentration is slightly higher in the case of a small molecular weight dextrin, but if the concentration is too high, aggregation between the starch or dextrin molecules will occur It is not easy to form a complex, it is preferably 0.01 to 20.0%, more preferably 10% or less, most preferably 3% or less, but is not limited thereto.

In another embodiment of the present invention, the functional material is not dissolved in a hydrophobic solvent, directly added to the starch or dextrin aqueous solution, characterized in that the method for producing a nano-sized composite combined with a starch and a functional material. To provide.

In a preferred embodiment of the present invention, the functional material has a hydrophobic property so that only a spiral structure can be included by forming a complex of a straight starch or dextrin molecule with a V-amylose form, and having useful functionality to a human body or an organism. Any known material may be used, but anthracenic, astaxanthin, alpha-carotene, beta-carotene, beta-apo-4'-carotenal, beta-apo-8'-carotenal, canthaxanthin, citranasanthin, creep Toxanthine, Dihydroplectananthine, Diatoxanthin, Fucoxanthin, Fucosantinol, Lactucaxanthin, Lutein, Lycopene, Neoxanthin, Neurosporanthin, Neurosporene, Ferridinine, Phytoene, Roadpin, Siphonoxanthin, spheroidine, spiriloxanthin, torulladine, freeolide, freeolide acetate, violaxanthin, zeaxanthin, nerol, nerolidol, citral, cinnamic aldehyde, citronerole , cis-3-hexanal, vanillin, isoamyl acetate, 1-octene-3-one, octyl acetate, cardaberine, hexanal, masoaralactone, menthol, methyl butyrate, mentone, pentyl butyrate, pentylpentano Eight, linalul, geraniol, decanal, 1-naphthol, fish oil, beeswax, D-limonene, vitamin A, vitamin E, coenzymecuten (Co-Q10), lecithin, DHA, EPA, capsaicin and hydrophobic drugs It is preferably, but not limited to, one selected from the group consisting of, or a mixture of the aforementioned substances.

In the embodiment of the present invention, as an example of the functional material, but beta-carotene and coQ10 was included in the nano-deck screen experiment to form a complex, 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 one embodiment of the present invention, the step of mixing the hydrophobic solution containing the functional material and the starch or dextrin aqueous solution or the complex material forming step by adding and mixing the functional material directly to the starch or dextrin aqueous solution, the melting of the functional material Preference is given to performing at temperatures higher than the temperature.

In the embodiment of the present invention, depending on the melting temperature of the functional material may be reacted directly or dissolved in a hydrophobic solvent. For example, CoQ10 can be directly reacted with dextrin solution because it melts and becomes liquid when reacted at 50 ° C or higher because the melting temperature is 50 ° C or lower. On the other hand, since beta carotene has a melting point of 181 ° C, it is dissolved in a hydrophobic solvent and then reacted with dextrin solution. Therefore, when the reaction is carried out at a temperature lower than the above range, the mobility of the starch molecules are lowered and the solubility of the starch is lowered to cause aggregation between starch molecules. When the reaction is carried out at a temperature higher than the above range, the formed starch complex may be melted again.

In one embodiment of the present invention was carried out at a reaction temperature of 50 ℃, in this case it is most preferred because the complex formation is easy with sufficient mobility of starch molecules.

In one embodiment of the present invention, the step of mixing the hydrophobic solution containing the functional material and the starch or dextrin aqueous solution or the complex material by adding the functional material directly to the starch or dextrin aqueous solution and mixing step 10 Preference is given to performing at a temperature of from < RTI ID = 0.0 > When the reaction is carried out at a temperature lower than the above range, the mobility of the starch molecules is lowered and the solubility of the starch is lowered to cause aggregation between the starch molecules. When the reaction is carried out at a temperature higher than the above range, the formed starch complex may be melted again.

In one embodiment of the present invention, the complex formation of step c) is preferably carried out through phase separation of the hydrophobic solution containing a functional material and the starch or dextrin aqueous solution.

In other words, the composite is generally synthesized by directly mixing starch molecules and clathrates. In this case, the crystal formation yield 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.

The hydrophobic solvent used in the preparation method of the present invention preferably has a component which does not form a complex with starch or has a lower complex forming ability than a functional material, and any hydrophobic solvent in which phase separation with water 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 (ethyl ether), petroleum ether ( petroleum ether), preferably selected from the group consisting of vegetable oils.

In one embodiment of the present invention, the step d) is capable of hydrolyzing 1-6 bonds with α-amylase, glucoamylase, α-glucosidase, β-amylase, which can degrade 1-4 bonds. It is preferable to decompose starch which is not involved in complex formation by using any one starch degrading enzyme or a mixture of the enzymes selected from the group consisting of iso-amylase and pullulanase, but is not limited thereto.

In another embodiment of the present invention, step d) does not participate in complex formation using any acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, malic acid, and acetic acid, or a mixture of acids. It is preferred, but not limited to, decomposing starch.

In the preparation method of the present invention, when dextrin is initially used, most dextrin molecules may be required to form a complex, so that the amount of enzyme and acid may be reduced, or the process may 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 additionally included washing and recovery process minimizes the structural change, it is preferable to use a solvent of alcohols such that the inclusion material is not removed from the complex, When the complex of the present invention is precipitated it can be recovered by simple filtration and centrifugation.

In the composite production method of the present invention, the recovered composite can be dried using various drying methods, such as vacuum drying, freeze drying, investment drying, hot air drying and spray drying. The composite of the present invention becomes a solid powder state by the drying process.

In the nanocomposite manufacturing method of the present invention, the obtained composite aqueous solution can be utilized directly in the product without undergoing the washing and recovery process.

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, the complex may have a functional material between the helical units according to the type of the functional material. The complex has nano-sized particles, and the helical structure of these particles is hydrophilic on the outside while hydrophobic on the inside. Various hydrophobic functional materials can be entrapped inside, and the entrapped materials are easily dissolved in water by the hydrophilic spiral outer structure. Therefore, it is possible to easily accommodate a variety of hydrophobic functional material can more efficiently deliver the hydrophobic functional food material or drug components, it is possible to suppress the oxidation or denaturation of these substances on the way. In addition, hydrophobic flavor components can be enclosed inside the helical structure, and these components can be prevented from volatilizing easily, and thus can be stored and delivered more stably. Therefore, the nano starch complex may be used to capture and deliver functional substances or pharmaceutical components 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. 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.

In another aspect, the present invention provides a nano-sized composite in which the starch and the functional material produced by the production method of the present invention is combined.

The complex obtained in the present invention is a complex in which a hydrophobic substance is enclosed by utilizing linear starch molecules or starch dextrins. Hydrophobic materials have been accommodated and stabilized, not just as nanoscale starch particles, and these complexes have the effect of enhancing functionality in a variety of applications by making these nanoparticles into small sized particles.

1 is a diagram illustrating a complex formation process in which linear starch or dextrin is conjugated to a functional material.

2 is a view showing a method for producing nanostarch particles using phase separation.

3 is a view showing the shape of the nanoparticles prepared by Example 1.

4 is a view showing the particle size distribution of the nanoparticles prepared by Example 1.

5 is a diagram showing an x-ray diffraction diagram of the nanoparticles prepared in Example 1. FIG.

6 is a view showing a particle size distribution of nanoparticles prepared in Example 4. FIG.

Hereinafter, the present invention will be described in more detail with reference to non-limiting examples. However, the following examples are described for the purpose of illustrating the present invention and the scope of the present invention is not to be construed as limited by the following examples.

Example 1.Preparation of Nano Dextrin-Betacarotene 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 stirred well after adding 1 mL of 36% HCl. 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. Beta carotene 15 mg was dissolved in 60 mL of isopropyl ether, and then slowly added the isopropyl ether solution 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 24 hours with stirring at 400 rpm. In addition, in order to accelerate the reaction, the composite was prepared in an open state without sealing the reaction solution.

3) Recovery of dextrin-beta carotene complex

After 24 hours the aqueous solution containing the complex was precipitated by high speed centrifugation (× 25,000 g) and then recovered. The reason for using isopropyl ether as a solvent of beta-carotene in this embodiment is that isopropyl ether is a solvent that dissolves beta-carotene well and phase-separates with water without forming a complex with starch.

Test Example  1. Beta-carotene content complexed with dextrin

100 mL of the nanodextrin-beta carotene complex solution prepared in Example 1 was heated at 121 ° C. for 20 minutes to destroy the complex, and then an isopropyl ether solution was added to the solution. Isoprephyll ether and aqueous solution will be phase separated and all beta carotene will be dissolved in isopropyl ether solution, and the beta carotene content in isopropyl ether solution is determined by UV-Visible Spectrophotometer (Ultrospec 2000 UV / Visible Spectrophotometer, Pharmacia Biotech, UK ) Was measured as a change in absorbance at 448 nm. As a result, approximately 90% (13.2 mg of 15 mg) of beta carotene complexed with dextrin.

Test Example  2. Observation of particle size and crystallinity

The particle size analyzer (Dynapro Titan, Wyatt Technology, SantaBarbara, CA) was used to measure the average diameter and size distribution of the particles prepared in the above examples. The nano-level starch particles were about 20% to 80 nm in size and about 10% were 100 nm or more. These results suggest that the nanoscale particles are agglomerated into some large mass.

Test Example  3. Particle Crystallinity

The crystallinity of the dextrin-betacarotene complex was measured using an X-ray diffraction analyzer (MO3XHF22 MAC science CO. Japan). Dextrin-beta-carotene complex showed V6 form crystallinity. V6 crystals form when helical complexes such as amylose, fats and alcohols form spiral complexes. These spiral crystals have a structure in which six glucose chains are consumed in one rotation, and beta carotene is enclosed within the spiral crystals. Can be confirmed.

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 15 mg of beta-carotene in 60 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 with stirring at 400 rpm for 24 hours at 50 ° C.

2) recovery of starch-beta carotene complex

After 24 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 decomposed and only the complexes remain. High speed centrifugation (× 25,000 g) then precipitated and recovered the starch complex.

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 complex 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 of the crystal was measured using an X-ray diffraction analyzer.

EXAMPLE  3. Nano Waxy Dextrin- Kokyuten  Preparation of the complex

1) Dextrin Manufacturing

After dissolving 1 g of waxy corn starch in 99 mL of distilled water, acetate buffer solution (1 M, pH 3.5, 1 mL) was added, and 30,000 units of isoamylase were added thereto, followed by hydrolysis 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. 400 mg of CoQ10 was added to the dextrin solution after

The reaction was carried out at 50 ° C. for 72 hours while stirring at 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. CoQ10 content of recovered complex is about 60 ~ 80 mg

It was confirmed that more than 60% of the added cocuten reacted with dextrin.

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 20-100 nm. In addition, the crystallinity of the dextrin-cocuten complex was measured using an X-ray diffractometer.

EXAMPLE  4. Nano Corn Dextrin- Kokyuten  Preparation of the complex

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. Then washed once with acetone and then dried for 12 hours at 40 ℃ and pulverized.

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 131 ° C. for 20 minutes. 100 mg of CoQ10 was added to the dextrin solution, followed by dissolution of CoQ10 for 1 hour at 70 ° C. with stirring at 550 rpm, and ultrasonication for 3 minutes, followed by reaction for 72 hours. 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 (× 25,000 g). The content of cocutene in the recovered complex was about 80-90 mg, and it was confirmed that 90% or more of the cocuten added was reacted with dextrin.

Test Example  1. complexed with dextrin Kokyuten  content

100 mL of the nanodextrin-cocuten complex solution prepared in Example 1 was heated at 121 ° C. for 20 minutes to destroy the complex, and then an isopropyl ether solution was added to the solution. Isoprephyll ether and aqueous solution will be phase separated and cocuten will all be dissolved in isopropyl ether solution, and the content of cocuten dissolved in isopropyl ether solution is measured using an ultraviolet-visible spectrophotometer (Ultrospec 2000 UV / Visible Spectrophotometer, Pharmacia Biotech, UK). It was measured by the change in absorbance at 275 nm. As a result of the measurement, approximately 80-90% cocutene added complexed with dextrin.

Test Example  2. Observation of particle size

The average diameter and particle size distribution of the composite prepared in Example 4 were measured using a particle analyzer (Dynapro Titan, Wyatt Technology, SantaBarbara, CA). The dextrin-cocuten complex dispersed in the solution was distributed into particles having an average diameter of 50 to 200 nm in size.

As can be seen by the above solution and the following examples, according to the present invention, nano-level particles can be prepared by complexing starch and starch dextrin with various hydrophobic materials.

Nano starch particles prepared by the method of the present invention is converted to be used in a variety of products by receiving the encapsulated hydrophobic material. 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 particles can be usefully applied as a functional material or a drug delivery material in the food, cosmetic and pharmaceutical industries. In addition, it is expected to be used as a substitute, coating, capsule, reinforcing agent, and the like.

Claims (15)

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

   b) dissolving the functional material in a hydrophobic solvent;

   c) mixing the hydrophobic solution containing the functional material with the starch or dextrin aqueous solution; And

   d) a method of preparing a nano-sized complex in which starch and a functional material are combined, comprising the step of changing the structure by enzymatic or acid treatment of the resultant of step c).
2. The method according to claim 1, wherein the starch or dextrin of step a) is prepared by dextrinizing starch, and the method of producing a nano-sized composite combined with a starch and a functional material.
3. 3. The dextrinization of claim 2, wherein the dextrinization comprises an α-amylase, a glucoamylase, an α-glucosidase, a β-amylase capable of degrading 1-4 bonds, and an iso-amylase capable of hydrolyzing 1-6 bonds. A method for producing a nano-sized complex in which a starch and a functional substance are combined, characterized in that the starch is dextrinized using any one starch degrading enzyme selected from the group consisting of pullulanase or a mixture of the enzymes.
4. 3. The starch according to claim 2, wherein the dextrinization is dextrinized with starch using any one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, malic acid and acetic acid or a mixture thereof. Method for producing a nano-sized composite combined with a functional material.
5. The method of claim 2, wherein the dextrinization is dextrinization of starch using micro ray or radiation.
6. The method of claim 1, wherein the concentration of starch or dextrin used in step a) is 0.01 to 20.0%.
7. According to claim 1, wherein the starch is 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, barley starch, soybeans ( pea starch, wheat starch, chamomile starch, sago starch, amaranth starch, tapioca starch, sorghum starch, brisket starch, banana starch, mung bean starch, eastern starch, kuzukiri starch, derivatives of these starches And a starch selected from the group consisting of amylose extracted from these starches.
8. The method of claim 1, wherein the functional material is not dissolved in a hydrophobic solvent, but directly added to the starch or dextrin aqueous solution and mixed.
9. The method of claim 1, wherein the functional material is antheraxanthin, asaxanthin, alpha-carotene, beta-carotene, beta-carotene, beta-apo-4'-carotenal (beta) -apo-4'-carotenal, beta-apo-8'-carotenoic acid, canthaxanthin, citranaxanthin, cryptoxanthin , Dehydroplectaniaxanthin, diatoxanthin, fucoxanthin, fucoxanthinol, lactucaxanthin, lutein, lycopene, neoxanthin (neoxanthin), neurorosporaxanthin, neurorosporene, neurosporene, peridinin, phytoene, rhodopin, siphonaxanthin, spheroidine , Spirilloxanthin, torralloodin, uriolide, uriolide acetate ( uriolide acetate, violaxanthin, zeaxanthin, nerol, nerolidol, citral, cinnaaldehyde, citronaldehyde, citronellol, cis-3- Cis-3hexenal, vanillin, isoamyl acetate, 1-octen-3-one, octyl acetate, cadaverine Hexanal, massoia lactone, menthol, methyl butyrate, menhone, pentyl butyrate, pentyl pentanoate, lina Linalool, geraniol, decanal, 1-naphthol, fish oil, beeswax, D-limonene, vitamin A, vitamin E, coenzyme A combination of starch and functional substances selected from the group consisting of cutene (Co-Q10), lecithin, DHA, EPA, capsaicin and hydrophobic drugs or mixtures of these substances; The method of size of the complex.
10. The method of claim 1, wherein the mixing of the hydrophobic solution containing the functional material and the starch or dextrin aqueous solution is performed at 10-100 ° C. Way.
11. The method of claim 8, wherein the adding of the functional material directly to the starch or dextrin aqueous solution and mixing is performed at 10-100 ° C. 10.
12. The method of claim 1, wherein the step d) comprises α-amylase, glucoamylase, α-glucosidase, β-amylase capable of breaking down 1-4 bonds, and iso-amylase capable of hydrolyzing down 1-6 bonds. And a nano-sized complex in which starch and a functional substance are combined, by using any one of the starch degrading enzymes selected from the group consisting of and a pullulanase or a mixture of the enzymes. Way.
13. The method of claim 1, wherein the d) step is used to decompose starch that does not participate in complex formation using any acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, malic acid and acetic acid or a mixture thereof. Method for producing a nano-sized composite combined with a starch and a functional material, characterized in that.
14. The method of claim 1, wherein the forming of the complex of step c) is performed by the phase separation of the hydrophobic solution containing the functional material and the starch or dextrin aqueous solution of the nano-sized composite combined with the starch and the functional material Manufacturing method.
15. A nano-sized composite in which starch prepared by the method of any one of claims 1 to 14 and a functional material are combined.

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