JP5070075B2 - Polymerized catechin nanofiber - Google Patents

Description

  The present invention relates to a nanofiber assembly containing a polymerized catechin and / or a polymerized catechin derivative.

Until now, the technique which manufactures a nanometer-sized polymer fiber by the electrospinning method is known (for example, patent document 1). This method will be briefly described as follows. As shown in FIG. 1, a container 2 storing a polymer solution 1 as a raw material and a target electrode 3 are provided. A nozzle 4 capable of discharging the polymer solution 1 is provided at the tip of the container 2. Here, when the polymer solution 1 is released from the nozzle 4 with a high voltage applied between the nozzle 4 and the target electrode 3, the polymer solution 1 moves from the nozzle 4 to the target electrode 3. A fibrous fiber is formed along the lines of electric force, and the nanofiber 5 is produced on the target electrode 3.
This method is characterized in that a fiber of the order of 10 nm to several hundred nm and a sheet or mat (nanofiber aggregate) in which the fibers are integrated can be produced.

  Since the diameter of the nanofiber is thin and the sheet or mat that is an aggregate of the nanofiber has a large porosity, a wide range of applications for various uses is considered. Since the nanofiber aggregate has a fine internal structure and surface structure, it has a large specific surface area, and exhibits excellent properties for use as, for example, an adsorbent. However, the polymer nanofibers produced by the electrospinning method have a smooth surface, and it is not always easy to decorate the surface and add functions. For example, if an inorganic substance is mixed in a polymer for the purpose of utilizing the function of the inorganic substance, the inorganic substance is embedded in the polymer of the nanofiber, and the original function of the inorganic substance may not be exhibited. is there.

In addition, research and development for producing nanofibers from materials such as polylactic acid and collagen using the electrospinning method has been carried out. Since such materials are excellent in biodegradability and are derived from living organisms, application to automobiles and home appliances, and applications to medicines, cosmetics, foods and hygiene products are considered.
US Pat. No. 6,656,394

Furthermore, in order to improve the functionality of the nanofiber, there may be a concept of combining a functional material with the nanofiber manufactured from polylactic acid or collagen. However, sufficient studies have not been made as to whether such products can actually be manufactured.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a nanofiber assembly containing a functional material and to provide a method for manufacturing such a nanofiber assembly. It is.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have applied the electrospinning method by combining a specific spinning base material and a functional substance, and thereby a functional material-containing nanofiber. The present inventors have found that an aggregate can be produced and have completed the present invention.

That is, the present invention is as follows.
(1) At least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, zein, gelatin, collagen, chitosan, and a group consisting of polymerized catechin and polymerized catechin derivative A nanofiber assembly comprising at least one functional substance selected.
(2) The nanofiber aggregate according to (1), wherein the functional substance is a polymerized catechin.
(3) The functional substance is one or more selected from the group consisting of cacao polyphenol, apple polyphenol, oolong tea polyphenol, grape polyphenol, amla polyphenol, and persimmon polyphenol. Nanofiber assembly.
(4) The nanofiber aggregate according to (1), wherein the functional substance is cocoon polyphenol.

(5) A nanofiber is produced by electrospinning at least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, zein, gelatin, collagen and chitosan. A method for producing nanofibers, which comprises containing at least one functional substance selected from the group consisting of polymerized catechins and polymerized catechin derivatives.
(6) The functional substance is one or more selected from the group consisting of cacao polyphenol, apple polyphenol, oolong tea polyphenol, grape polyphenol, amla polyphenol, and persimmon polyphenol. Nanofiber manufacturing method.
(7) The method for producing nanofibers according to (5), wherein the functional substance is cocoon polyphenol.

(8) From at least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, zein, gelatin, collagen, chitosan, and a group consisting of polymerized catechin and polymerized catechin derivative A method for producing nanofibers, comprising producing nanofibers from a material containing at least one functional substance selected by electrospinning.
(9) The functional substance is one or more selected from the group consisting of cacao polyphenol, apple polyphenol, oolong tea polyphenol, grape polyphenol, amla polyphenol, and persimmon polyphenol. Nanofiber manufacturing method.
(10) The method for producing nanofibers according to (8), wherein the functional substance is cocoon polyphenol.

  According to the present invention, a nanofiber assembly containing a functional substance can be produced. This nanofiber aggregate has both the functions of nanofibers and the functions of polymerized catechins and / or polymerized catechin derivatives, so it has antioxidant, antibacterial, antiviral, and deodorant effects. Has a harmful substance adsorption action. Therefore, medical parts such as artificial skin, filters for air conditioners, automobiles, air cleaners, hygiene products such as masks, gauze, packs, sheets, medical care, NDS (Nutrition Delivery System: Minerals, Vitamins, etc.) New system aimed at supplying nutritional materials safely and efficiently into the living body) Food materials such as base materials, deoxygenated base materials, and fast-dissolving base materials, functional bases, bases for dirt removal It can be applied to cosmetics such as materials.

  Next, embodiments of the present invention will be described in detail. The technical scope of the present invention is not limited by the following embodiments, and various modifications can be made without changing the gist of the invention. Further, the technical scope of the present invention extends to an equivalent range.

The polylactic acid used in the present invention is a kind of biodegradable plastic in which lactic acid (CH ₃ CH (OH) COOH) is used as a unit and a plurality of lactic acids are linked to have a high molecular weight. Lactic acid as a material for producing polylactic acid can be produced from plants (for example, corn, bonito, sugar cane, beet, sweet potato, etc.). In order to produce polylactic acid, lactic acid is generally cyclized into lactide, which is subjected to ring-opening polymerization to obtain polylactic acid, but in the present invention, it is not dependent on the method for producing polylactic acid.

Two types of optical isomers, L-type and D-type, are known for lactic acid as a simple substance constituting polylactic acid. The present invention can also be used for polylactic acid produced using either L-type or D-type lactic acid as a unit (or for polylactic acid containing L-type and D-type in any ratio).
Egg white peptide means a peptide obtained by appropriately hydrolyzing egg white. Egg whites are those obtained by removing egg yolk from whole eggs (for example, chicken eggs), those obtained by splitting eggs with shells, those obtained by thawing frozen egg whites, those obtained by concentrating them, and egg white powder being returned with water. Any of them may be used, and is not particularly limited, but raw egg white liquid or frozen egg white liquid is preferable from the viewpoint of processability. In order to hydrolyze the egg white, for example, it can be treated with a suitable hydrolase. Such an enzyme is not particularly limited as long as it is a plant-derived, animal-derived, or bacterial-derived protease (proteolytic enzyme), but a protease extracted from cells of the genus Bacillus may be used. It is preferable to use a protease extracted from one or more cells selected from the group consisting of Bacillus licheniformis, Bacillus thermoproteolyticus Roko, and Bacillus subtils.

  The conditions for the protease treatment are not particularly limited, but the hydrolysis temperature is preferably 55 ° C. to 65 ° C. within a pH range of 7-10. The degree of degradation of the enzyme hydrolyzate is not particularly limited, but it is preferably degraded until the amino group amount is 7 to 20 times that of the raw protein, and the average amino acid chain length of the enzyme hydrolyzate is 2 or more and a free amino acid content of 20% or less is preferable, and the average amino acid chain length of the enzyme hydrolyzate is preferably 2-15. The amount of amino groups means the amount of amino groups of the end of the protein or protein hydrolyzate and the lysine residue. The amino group amount, average amino acid chain length, and free amino acid content can be measured by a formol titration method, a TNBS coloring method, a ninhydrin coloring method, or the like. Moreover, as an egg white peptide, Profix (trademark registration: Taiyo Kagaku Co., Ltd.) can be used.

Zein is also called zein. It is a major protein of corn seed and belongs to prolamin. Prolamin is a generic term for proteins belonging to simple proteins, soluble in 60% to 90% ethanol, and insoluble in 90% or more ethanol, water, and neutral salt solutions. In addition, wheat gliadin, barley hordein and so on. Zein is composed of various molecular species, and main components include those having a molecular weight of 22,000 and a molecular weight of 19000.
Gelatin is a general term for substances in which the three-dimensional structure of collagen contained in higher animals is broken. Gelatin is very soluble in water. In the present invention, any animal species and collagen type can be used.

Collagen means the main protein component that constitutes the connective tissue of animals. Mammals account for nearly 30% of the body's total protein. Collagen consists of 10 or more protein super families such as type I and type II, and has a high content of glycine and proline. In the present invention, any type of collagen or mixture can be used.
Chitosan mainly means β-1,4-polyglucosamine and is a deacetylated product of chitin. Although a β-1,4-polyglucosamine structure is main, it is produced by melting chitin with concentrated alkali, so there may be some structural changes.

  Polymerized catechins are polyvalent phenols such as water-soluble catechins, epicatechins, gallocatechins, epigallocatechins, catechin gallates, epicatechin gallates, gallocatechin gallates, epigallocatechin gallates, etc. Means a combination of about 2 to 50. As described above, the polymerized catechin includes a plurality of types. In the present invention, any polymerized catechin derivative to which any of these molecules (including the same or different species) is bonded can be used.

  Persimmon polyphenol means about 1% -2% soluble tannin (oyster tannin), which is called “persimmon astringent” contained in astringent persimmon, and shows a strong astringency. In sweet persimmon or astringent persimmon (barrel persimmon or dried persimmon), these persimmon polyphenols have changed to insoluble ones and do not feel astringency.柿 Polyphenol is a high molecular compound with a molecular weight of about 15,000 which is a condensate of 12-30 molecules of epicatechin, catechin gallate, epigallocatechin and gallocatechin gallate in a ratio of 1: 1: 2: 2 and is based on delphinidin. It is classified into proanthocyanidin polymer or condensed tannin. Along with immature bananas and cabbage beans, it is considered to be a fruit and vegetables strong astringency component.

  Oolong tea polyphenol is a component unique to oolong tea produced by polymerization of catechins in the process of semi-fermenting tea leaves, and is considered to have lipase inhibitory activity. As a representative component of oolong tea polyphenol, the chemical structure of epigallocatechin-3-gallate (EGCG) dimer has been confirmed.

  Apple polyphenol includes various catechins and various polyphenols such as chlorogenic acid, and has been announced to have quality maintaining functions such as an antioxidant effect and physiological functions such as caries prevention. Apple polyphenols are also found in the pulp, but the skin is more abundant. Apple polyphenols are said to be effective for dieting because they have functions such as reducing cholesterol that causes ischemic heart disease and suppressing fat absorption. In addition, apple polyphenols are expected to be effective against allergic symptoms such as atopic dermatitis and hay fever because they have an antioxidant action and a function of suppressing the release of histamine, which is a cause of itching. Apple polyphenols have been confirmed to inhibit plaque adhesion and formation, and the component group "procyanidins" contained in apple polyphenols has the effect of suppressing cancer cell growth and tumor growth. It is said. Procyanidins are substances in which a large number of catechins are bound. Epicatechin is the main structural unit in apples, and the presence of up to 15-mer has been confirmed.

  Cocoa polyphenols include polyphenol products including proanthocyanidins, and more particularly procyanidins extracted from cocoa beans and their derivatives.

  Grape polyphenols are polyphenols extracted and purified from grape berries, seeds and peels, and are known to have proanthocyanidins as the main components and have particularly strong antioxidant power.

  Amla polyphenols are polyphenols extracted and purified from Amla berries, seeds and pericarp, and are known for their strong antioxidant activity, mainly composed of ellagitannins.

The nanofiber of the present invention means a fiber having a single yarn diameter of about 1 nm to about 800 nm, and a collection of the fibers is called a nanofiber aggregate. The nanofiber aggregate can be formed into a one-dimensionally oriented long fiber or spun yarn shape, but when it is produced by electrospinning, it is obtained as a two-dimensional aggregate as a nonwoven fabric. The nanofiber aggregate obtained as a non-woven fabric can be used as an artificial skin, filter, mask, gauze, or other base material.
Although the nanofiber aggregate of the present invention can be produced by various methods for producing nanofibers, it is particularly preferable to use an electrospinning method (also referred to as an electrospinning method or an electrostatic spinning method). In this case, the polymerization type catechin and / or the polymerization type catechin derivative are prepared in advance by a method of producing a nanofiber assembly in the state of coexisting with a spinning substrate, There is a method of containing a polymerization type catechin and / or a polymerization type catechin derivative.
In order to produce a nanofiber aggregate in advance and to contain the polymerized catechin and / or polymerized catechin derivative here, first, the spinning substrate is prepared by using an appropriate solvent (an inorganic solvent such as water, an organic solvent (protic). In a polar solvent and aprotic polar solvent), and the electrospinning method is carried out with this solution. The electrospinning method can be influenced by factors such as the concentration of the spinning substrate, the type of solvent, the diameter of the needle, the injection distance, the rotation speed, the voltage, and the injection speed. In order to actually manufacture a nanofiber assembly, the above factors can be combined appropriately.
The nanofiber aggregate thus produced is allowed to contain a polymerization catechin and / or a polymerization catechin derivative. As such a method, for example, a method of immersing a nanofiber aggregate in a solution in which a polymerized catechin and / or polymerized catechin derivative is dissolved, or a polymerized catechin and / or polymerized catechin derivative in a nanofiber aggregate Examples thereof include a method of dripping and spraying a solution in which is dissolved.
In the case of producing a nanofiber assembly by the above method, it is preferable to use a protein-based substance (for example, egg white peptide, whole egg peptide, egg yolk peptide, zein, gelatin, etc.) as a spinning substrate. This is because when a nanofiber assembly is produced from such a substance, the polymerized catechin and / or polymerized catechin derivative is easily bonded to the nanofiber.

  Further, in order to produce a nanofiber aggregate in the state of coexisting with the spinning base material in advance, the spinning base material and the functional material are mixed with an appropriate solvent (inorganic solvent such as water, organic solvent (protic polar solvent, non-polar solvent, etc.). In a protic polar solvent). At this time, (1) a method in which only the spinning substrate is dissolved in an appropriate solvent, while a functional substance is dissolved in another solvent, and both solutions are mixed later, or (2) the spinning substrate and functionality There is a method in which both substances are dissolved in the same solvent. The appropriate method (1) or (2) can be selected depending on the combination of the spinning substrate and the functional substance. Thus, the electrospinning method is performed on the material containing the spinning base material and the functional substance. The electrospinning method can be influenced by factors such as the concentration of the spinning substrate, the type of solvent, the diameter of the needle, the injection distance, the rotation speed, the voltage, and the injection speed. In order to actually manufacture a nanofiber assembly, the above factors can be combined appropriately.

EXAMPLES Next, although an Example and a test example demonstrate this invention in detail, this invention is not limited by these Examples and a test example.
<Example 1> Production of nanofiber assembly containing polylactic acid and cocoon polyphenol 0.297 g of polylactic acid (weight average molecular weight (Mw) 123,284, number average molecular weight (Mn) 61,323, Mw / Mn = 2.010, trade name Lacia (R) H-900, manufactured by Mitsui Chemicals, Inc.) and 2.703 g of hexafluoroisopropanol (HFIP) were added to the sample bottle 1. A magnetic stirrer was placed in the sample bottle 1, and the polylactic acid was completely dissolved using the stirrer at room temperature (20 ° C.-25 ° C.) with stirring overnight (about 10 hours or more).

In another sample bottle 2, add 1.5g of persimmon (odorless persimmon: manufactured by Osugi-type Paper Industry Co., Ltd.) and 1.5g of dimethylformamide (DMF), and use a vortex mixer to vibrate until mixed. Stir.
3.0 g of the polylactic acid solution in the sample bottle 1 and 3.0 g of the persimmon astringent solution in the sample bottle 2 were mixed in another sample bottle 3 and vibrated and stirred using a vortex mixer until they were mixed.

After injecting the sample solution in the sample bottle 3 into the syringe, the bubbles in the syringe were expelled. This syringe was set in a syringe pump of an electrospinning apparatus, and an electrospinning method was performed under the following conditions.
As an electrospinning apparatus, the apparatus of Imoto Seisakusho Co., Ltd. was used. 21G (made by Hoshiseido Medical Equipment Co., Ltd.) was used as the syringe needle, and the injection distance was 10 cm, the rotation speed was 80 rpm, the voltage was 20 kv, and the injection speed was 2 mL / hr.
The results are shown in FIGS. As shown in the figure, when a polylactic acid-polymerized catechin system was used, good nanofibers were produced by the electrospinning method. This nanofiber had an outer diameter of about 100 nm to 500 nm.

  Thus, according to the present Example, the nanofiber assembly containing a functional substance was able to be manufactured. This nanofiber aggregate has both the functions of nanofibers and the functions of polymerized catechins and / or polymerized catechin derivatives, so it has antioxidant, antibacterial, antiviral, and deodorant effects. Has a harmful substance adsorption action. Therefore, medical parts such as artificial skin, filters for air conditioners, automobiles, air cleaners, hygiene products such as masks, gauze, packs, sheets, medical care, NDS (Nutrition Delivery System: Minerals, Vitamins, etc.) New system aimed at supplying nutritional materials safely and efficiently into the living body) Food materials such as base materials, deoxygenated base materials, and fast-dissolving base materials, functional bases, bases for dirt removal It can be applied to cosmetics such as materials.

It is a figure explaining the outline | summary of an electrospinning method.

2 is an electron micrograph showing the results of Example 1. FIG.

2 is an electron micrograph showing the results of Example 1. FIG.

Claims (6)

  At least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, and zein, and selected from the group of cacao polyphenol, apple polyphenol, oolong tea polyphenol, grape polyphenol, amla polyphenol, and straw polyphenol And a functional substance that is one type or two or more types.   2. The nanofiber assembly according to claim 1, wherein the functional substance is cocoon polyphenol.   A nanofiber is produced by electrospinning at least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, and zein, and cocoa polyphenol, apple polyphenol, oolong tea is produced on the nanofiber. A method for producing nanofibers, comprising one or more functional substances selected from the group consisting of polyphenol, grape polyphenol, amla polyphenol, and persimmon polyphenol.   The method for producing nanofiber according to claim 3, wherein the functional substance is cocoon polyphenol.   At least one spinning substrate selected from the group consisting of polylactic acid, egg white peptide, whole egg peptide, egg yolk peptide, and zein, and selected from the group of cacao polyphenol, apple polyphenol, oolong tea polyphenol, grape polyphenol, amla polyphenol, and straw polyphenol A method of producing nanofibers, comprising producing nanofibers from a material containing one or more functional substances by electrospinning.   6. The method for producing nanofibers according to claim 5, wherein the functional substance is cocoon polyphenol.