WO2006101106A1

WO2006101106A1 - Precious metal nanocolloid solution

Info

Publication number: WO2006101106A1
Application number: PCT/JP2006/305650
Authority: WO
Inventors: Minenobu Okayama
Original assignee: Apt Co., Ltd.
Priority date: 2005-03-23
Filing date: 2006-03-22
Publication date: 2006-09-28
Also published as: JPWO2006101106A1; TW200704404A

Abstract

A precious metal nanocolloid solution comprising nanoparticles of a precious metal, such as platinum, gold or a mixture thereof, and a polysaccharide derived from natural products, such as pectin and chitosan. The precious metal nanocolloid solution retains high reactivity as a precious metal catalyst, excelling in cellular intake performance, and is free from problems, such as unpleasant odor. Further, there is provided a superoxide anion scavenger comprising the precious metal nanocolloid solution.

Description

Specification

Precious metal nano colloid solution

Technical field

[0001] The present invention relates to a noble metal nanocolloid solution containing nanoparticles of noble metals such as platinum and having high superoxide-on erasing ability.

Background art

[0002] A platinum nanocolloid solution containing platinum nanoparticles and a polyacrylate and having a concentration that halves superoxide-one is 200 mol Z liter or less is known (International Publication WO2005 / 023467) . In a preferred embodiment of the present invention, polyacrylic acid salt (sodium or potassium salt) is used as a protective material, and R value (ratio of moles of polyacrylate converted to monomer units and moles of platinum). Prepare a platinum nanocolloid solution so that is between 80 and 180. The particle size of 90% or more of platinum nanoparticles contained in this platinum nanocolloid solution is distributed between 0.1 and 10 nm. As a binary nanocolloid solution containing a noble metal, JP-A-9-225317 discloses use of a catalyst containing nickel and a noble metal, particularly as a hydrogenation catalyst. In a preferred embodiment of the invention described in JP-A-9-225317, a bull polymer having a cyclic amide structure as a protective material, particularly polyvinyl pyrrolidone, particularly poly N-vinyl-2-pyrrolidone, has the highest activity. It is preferred because it becomes a catalyst, and the R value (molar ratio of monomer to total metal) is 0.1 to 100, preferably 1 to 20! /.

[0003] However, all of the above-mentioned noble metal nanocolloid solutions proposed so far have a low R reaction efficiency as a catalyst for a noble metal having a large R value, and there is little uptake of noble metal particles into cells. Has the disadvantages. For example, according to the study by the present inventors, these noble metal nanocolloid solutions have a short time (within 1 minute) of superoxide-on elimination ability, ability to access cell membranes, or target ability with vitamin C. It has been found that it may be inferior in comparison. Further, the protective material such as polyacrylate and polyvinylpyrrolidone used in the noble metal nanocolloid solution disclosed in the above International Publication WO2005 / 023467 and Japanese Patent Laid-Open No. 9-225317 has a problem that it has a specific unpleasant odor. There is also. Reason for the above Therefore, it is desired to provide a noble metal nanocolloid solution that retains high reaction efficiency as a noble metal catalyst, has excellent intracellular uptake, and avoids problems such as unpleasant odor.

[0004] There is a report that chitosan is used in the preparation of gold nanocolloid solution (K. Esumi, Colloids and Surfaces B: Biointerfaces, 32, pp.117-123, 2003). However, it is not suggested or taught to have high activity as a superoxide-one scavenger. As for binary nanocolloids of gold and platinum, hydrogen generation from water by visible light (A. Harriman, J. chem. Soc, Commun., 24, 1990) is known. However, Toshima, N., Hirakawa. K., Polymer J. 3, pp. 1127-1132, 1999) reported the relationship between the combination of the two and the hydrogen evolution. These documents do not suggest or teach that they have high activity as superoxide-on scavengers.

[0005] Also, alginate, starch, glycogen, gelatin, pectin, chitosan, chitin, cellulose and its derivatives, gum arabic, locust bean gum, cara gum, gum tragacanth, gati gum, agar agar, power laginin, locust bean gum , Guar gum, and xanthan gum group strength is a hydrocolloid dressing containing a selected hydrocolloid, and a sachet containing nanocrystalline platinum is known (Japanese Patent Publication No. 2004-529930). However, the term “hydrocolloid” in this invention means a polymer (synthetically prepared or naturally occurring) that can form a thickening gel in the presence of water and a polyol (swelling agent). Polymer), and the swelling agent has the action of swelling the selected hydrocolloid to form a gel phase, so that it is a metal like a protective material used in the preparation of nanocolloids. It is not in a state of being coordinated with.

Non-patent document 1: Colloids and Surfaces B: Biointerfaces, 32, pp.117-123, 2003 Non-patent document 2: J. Chem. Soc, Commun., 24, 1990

Non-Patent Document 3: Polymer J. 3, pp. 1127-1132, 1999

Patent Document 1: International Publication WO2005 / 023467

Patent Document 2: Japanese Patent Laid-Open No. 9-225317

Patent Document 3: Japanese Translation of Special Publication 2004-529930 Disclosure of the invention

Problems to be solved by the invention

[0006] An object of the present invention is to provide a novel noble metal nanocolloid solution. More specifically, it is an object of the present invention to provide a noble metal nanocolloid solution that retains high reaction efficiency as a noble metal catalyst, has excellent intracellular uptake, and has no problems such as unpleasant odor.

Means for solving the problem

[0007] As a result of intensive studies to solve the above-mentioned problems, the present inventors obtained a precious metal nanocolloid solution using a natural product-derived polysaccharide such as chitosan or bectin as a protective material. It was found that the noble metal nanocolloid solution retains high reaction efficiency as a noble metal catalyst and is excellent in cellular uptake. The inventors have found that this noble metal nanocolloid solution can be used as a superoxide-on scavenger having extremely high activity. The present invention has been completed based on the above findings.

That is, according to the present invention, there is provided a superoxide-on scavenger comprising a noble metal nanocolloid solution containing noble metal nanoparticles and a natural product-derived polysaccharide.

According to a preferred embodiment of the present invention, the above superoxide-on erasing agent having an R value in the range of 3 to 4, the above superoxide-on erasing agent comprising two kinds of noble metals consisting of platinum and gold as noble metals The above superoxide anion scavenger is provided wherein the natural product-derived polysaccharide is chitosan, pectin, or a mixture thereof. From another viewpoint, there is a method for eliminating superoxide-one in the living body of mammals including humans, in which a noble metal nanocolloid solution containing noble metal nanoparticles and a natural product-derived polysaccharide is administered to mammals including humans. There is provided by the present invention a method comprising the steps of:

Furthermore, the present invention provides a beverage or food containing a noble metal nanocolloid solution containing noble metal nanoparticles and a natural product-derived polysaccharide.

Brief Description of Drawings

[0009] [Fig.1] Chitosan / platinum / gold nanocolloid solution with different gold content It is the figure which showed the one peroxyd-on residual rate.

FIG. 2 is a graph showing the percentage of remaining superoxide-on when the content of gold is changed in a pectin / platinum gold nanocolloid solution.

FIG. 3 is a graph showing the superoxide-on residual ratio when chitosan concentration is changed in a chitosan / platinum / gold nanocolloid solution (platinum: gold = 1: 1).

FIG. 4 is a graph showing the superoxide-on residual rate when the pectin concentration is changed in a pectin / platinum / gold nanocolloid solution (platinum: gold = 1: 1).

FIG. 5 is a graph showing the results of measuring the superoxide-on residual ratio for a pyotinchitosan / platinum / gold nanocolloid solution (platinum: gold = 1: 1).

FIG. 6 is a diagram showing the results of measuring the pH stability of platinum nanocolloid (PAA-Pt) using platinum nanocolloid solution (CP-PT) and polyacrylic acid of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The noble metal nanocolloid solution contained in the superoxide-on scavenger of the present invention is characterized by containing noble metal nanoparticles and a natural product-derived polysaccharide.

The type of the noble metal is not particularly limited, and any of gold, ruthenium, rhodium, palladium, osmium, iridium, or platinum may be used, but a preferable noble metal is gold, ruthenium, rhodium, palladium, or platinum. Of these, gold or platinum is preferred. It is also preferable to use a combination of gold and platinum. When preparing a noble metal nanocolloid solution containing two or more kinds of noble metals, a mixture containing two or more kinds of noble metal fine particles or an alloy of two or more kinds of noble metals can be used. In the noble metal nanocolloid solution of the present invention, one or more kinds of metal nanoparticles other than the noble metal may be present.

As the natural product-derived polysaccharide, for example, a natural product-derived polysaccharide having a free carboxyl group or amino group in the molecule is preferable. For example, alginic acid, hyaluronic acid, chitin 'chitosan, pectin (pectinic acid and pectinic acid), mannuronic acid, N-acetyl darcosamine, D-galatatopyranosyluronic acid, glucuronic acid, darcosamine, N-acetyl Ability to mention darcosamine, methoxylated D-galatatopyranosyluronic acid, rhamnogalataturonane, cyclodextrin, amylopectin, methylcellulose, etc. It is not limited to. Of these, alginic acid, chitin 'chitosan, hyaluronic acid, pectin (including high methoxyl pectin and low methoxyl pectin, including misalignment), etc. are preferred, and low methoxyl pectin is most preferably used. The power that can be done. You can use two or more natural product-derived polysaccharides in combination!

[0012] In the superoxide-one scavenger of the present invention, the natural product-derived polysaccharide acts as a protective material for the noble metal nanocolloid. The natural product-derived polysaccharide may be subjected to appropriate chemical modification. For example, it may be chemically modified so that it can be combined with other physiologically active substances through an appropriate spacer as required. For example, chitosan can use polysaccharides derived from natural products bound with piotin, etc. After preparing a noble metal nanocolloid solution, various bioactive substances are bound to avidin, and noble metal nanocolloid solution containing the bioactive substance is prepared. Can be prepared. Pectin has a characteristic that it is soluble as much as possible, and there are no restrictions on the blending range, it has many divalent metal ions, and it is stable for a long time even in hard water, which is particularly advantageous for food applications. In addition, the activity of precious metal nanocolloids that are not affected by pH is more stable than that of sodium polyacrylate that has been used in the past.

[0013] The particle size of the noble metal nanoparticles contained in the noble metal nanocolloid solution is not particularly limited, but nanoparticles having an average particle size of 50 nm or less can be used, preferably the average particle size is 20 nm or less, More preferably, nanoparticles having an average particle size of 10 nm or less, particularly preferably an average particle size of about 6 to 6 can be used. It is also possible to use finer nanoparticles. It is preferable that 90% or more of the noble metal nanoparticles have a particle size distribution in the range of 0.1 nm to 10 nm.

[0014] Various methods for producing transition metal fine particles, preferably noble metal fine particles are known (for example, Japanese Patent Publication No. 57-43125, Japanese Patent Publication No. 59-120249, and Japanese Patent Application Laid-Open No. 9-225317, JP-A-10-176207, JP-A-2001-79382, JP-A-2001-122723, etc.), those skilled in the art refer to these methods and include them in the superoxide-on eraser of the present invention. The precious metal nanocolloid solution can be easily prepared. For example, as a method for producing noble metal nanoparticles, a chemical method called a precipitation method or a metal salt reduction reaction method, or a physical method called a combustion method can be used. Sue of the present invention The noble metal nanocolloid solution contained in the peroxide-on scavenger may contain nanoparticles prepared by any method, but it is a metal salt reduction reaction method from the viewpoint of ease of production and quality. It is preferable to use prepared nanoparticles.

[0015] In the metal salt reduction reaction method, for example, an aqueous solution or an organic solvent solution of a water-soluble or organic solvent-soluble noble metal salt or noble metal complex is prepared, and a natural product-derived polysaccharide is added to this solution. By adjusting the pH to 9 to 11 and heating to reflux in an inert atmosphere, reduction can be performed to obtain a noble metal nanocolloid solution containing noble metal nanoparticles. The type of water-soluble or organic solvent-soluble salt of the noble metal is not particularly limited, but for example, acetate, chloride, sulfate, nitrate, sulfonate, phosphate, etc. can be used. A complex may be used. The amount of the natural product-derived polysaccharide is not particularly limited, but is usually about 0.005 to 0.1% by weight, preferably about 0.01 to 0.025% by weight, based on the total weight of the solution. In the above reaction, various surfactants such as anionic, non-ionic, or fat-soluble surfactants may be used. When the reduction is performed using alcohol, ethyl alcohol, _n -propyl alcohol, n-butyl alcohol, n-amyl alcohol, ethylene glycol, or the like is used. However, the method for preparing the noble metal nanoparticles is not limited to the method described above.

[0016] Typically, a reducing agent such as alcohol, hydrazine, sodium tetrahydroborate, or citrate is added to an aqueous solution of a noble metal salt and heated near the boiling point of the solvent, solvent reflux, ultraviolet irradiation, After the noble metal reduction reaction is combined with ultrasonic irradiation, the solvent is removed to dryness, and the resulting noble metal nanoparticles are suspended in a desired solvent to prepare a noble metal nanocolloid solution. k. In the noble metal nanocolloid solution contained in the superoxide-one quencher of the present invention, the dispersion medium is preferably substantially water-powered, but contains a small amount of an organic solvent mixed with water such as ethanol or glycerin. And!

[0017] As the superoxide-on scavenger of the present invention, the noble metal nanocolloid solution prepared by the above method may be used as it is. The term “noble metal nanocolloid solution” used herein includes an aqueous dispersion in which noble metal nanoparticles are associated to form a cluster. The term “nano” generally refers to the average particle size of noble metal fine particles. This means that it can be measured on the order of nanometers, but it should not be interpreted in a limited way in any way. For example, fine particles having an average particle size of about 0.01 nm are also included in the range of nanoparticles used in the present specification.

[0018] Without being bound to any particular theory, the use of a natural product-derived polysaccharide such as chitosan or pectin as a protective material allows the noble metal nano-particles contained in the superoxide-on scavenger of the present invention. The colloidal solution has an R value of less than 80, preferably less than 40, more preferably less than 5, particularly preferably in the range of 3 to 4, which is much smaller than conventional noble metal nanocolloid solutions. (See Information Association “Synthesis of Metal Nanoparticles”, Control Technology and Application Development (published on December 22, 2004)). In the present invention, the R value means the ratio between the number of moles of the natural product-derived polysaccharide and the number of moles of platinum converted per monomer unit). Due to this property, the superoxide-one scavenger of the present invention is characterized in that the reactivity of the noble metal nanoparticles is extremely high and the cell accessibility is very high. In addition, the initial reaction within 1 minute is improved, and the precious metal nanocolloid solution can be efficiently prepared.

[0019] The superoxide-one-eliminating agent of the present invention can be administered as a pharmaceutical to mammals including humans, and can exert the superoxide-one-eliminating action in vivo. Further, the superoxide anion scavenger of the present invention can be used as a beverage having a superoxide anion erasing action, particularly as drinking water. In addition, the superoxide-on-eliminating agent of the present invention is added to foods or used in the manufacture of processed foods to prepare foods containing the superoxide-on-eliminating agent of the present invention as health foods. Can also be used. Furthermore, the superoxide-on-eliminating agent of the present invention can exert a skin beautifying effect or a whitening effect by adding it to cosmetics, or can be used for the preparation of medical devices or dental materials, or for the medium for cell culture. It can also be used for preparation.

Example

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the following examples.

Example 1 In a 100 mL eggplant flask, 2 mg of chitosan (Yaizu Suisan Chemical Co., Ltd., COS-Y, 12.4 ^ mol) and 19.7 mL of purified water (milli-Q) were added and stirred for 10 minutes at room temperature. hydrate solution 0.2 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) was added. After stirring at room temperature for 60 minutes, hold 0.1 mL of cooled NaBH aqueous solution (Wako Pure Chemical Industries, 0.4 M).

Four

The mixture was further stirred for 30 minutes, and then left to stand to obtain a red transparent solution (chitosan / gold nanocolloid solution, 166 / z M). The R value of this chitosan / gold nanocolloid solution was measured according to the method described in the Technical Information Association “Synthesis of Metal Nanoparticles” Preparation, Control Technology and Application Development ”to be 3.7.

[0021] Example 2

Tetrachloroethene mouthpiece acid tetrahydrate aqueous solution 0.2 mL of tetrachloroethene port chloroplatinic acid hexahydrate solution 0.2 m L (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} / z mol) was changed to the Example 1 Similarly, a chitosan / platinum nanocolloid solution was obtained.

Example 3

In Example 1, in place of the tetrachloroethene mouthpiece acid tetrahydrate aqueous solution 0.2 mL, tetrachloroethene mouthpiece acid tetrahydrate aqueous 0.1 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) and tetrachloroethene port chloroplatinic acid hexahydrate solution 0.1 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) except for using a mixture of, in the same manner as in example 1 to obtain a chitosan / platinum-gold nano colloid solution . Similarly, chitosan / platinum / gold nanocolloid solutions having different gold contents were prepared by using mixtures having different ratios of tetrachlorodiaurate tetrahydrate aqueous solution and tetrachlorodioctaplatinate hexahydrate aqueous solution.

[0022] Example 4

To a 100 mL eggplant flask, add 2 mg (petech foods, 12.4 mol) of pectin and 19.7 mL (milli-Q) of purified water and stir at room temperature for 10 minutes. 0 .2 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) to give a mosquito卩. After stirring for 60 minutes at room temperature, add 0.1 mL of cooled NaBH aqueous solution (Wako Pure Chemical Industries, 0.4 M) and stir for another 30 minutes.

Four

Stirring was continued, and then the mixture was allowed to stand to obtain a red transparent solution (pectin / gold nanocolloid solution, 166 μΜ). When the R value of this pectin / gold nanocolloid solution was measured according to the method described in Example 1, it was 3.7. [0023] Example 5

Tetrachloroethene mouthpiece acid 4 hydrate aqueous solution 0.2 mL tetrachloroethene port chloroplatinic acid hexahydrate solution 0.2 m L in the same manner as (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) Example 4 was changed to A pectin / platinum nanocolloid solution was obtained.

Example 6

In Example 4, instead of tetrachloroethene mouthpiece acid tetrahydrate aqueous solution 0.2 mL, tetrachloroethene mouthpiece acid tetrahydrate aqueous 0.1 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) and tetrachloroethene port chloroplatinic acid hexahydrate solution 0.1 mL (manufactured by Wako Pure Chemical Industries, ^{Ltd., 1.66 X 10- 2 M, 3.32} mol) except for using a mixture of, in the same manner as in example 1 to obtain a chitosan / platinum-gold nano colloid solution . In the same manner, pectin / platinum / gold nanocolloid solutions with different gold contents were prepared using mixtures having different ratios of tetrachlorodiaurate tetrahydrate aqueous solution and tetracroloplatinic acid hexahydrate aqueous solution. .

[0024] Example 7

The superoxide-on elimination action of the noble metal nanocolloid solutions prepared in Examples 1 to 6 was investigated. The hypoxanthine (HXN) / xanthine oxidase (XOD) system was used to evaluate the superoxide-on scavenging action.

(1) 50 L solution containing 5.5 mM hypoxanthine in 200 mM phosphate buffer (pH 7.5)

(2) DMPO (5,5-Dimethyl-1-pyrroline-Ν-oxide) 15 L

(3) Solution containing 100 L sample in purified water (only purified water for control)

(4) 50 μL of a solution containing 0.2 U / mL XOD in 200 mM phosphate buffer (pH 7.5) (stored on ice to prevent inactivation)

The measurement was performed 45 seconds after mixing the above (1) to (4). Measurement conditions are as follows Measuring instrument: JES—FA100

Frequency: 9420 MHz (value is not constant and moves slightly)

FIELD CENTER: 335.6 mT, Width = +/— 5.000 mT

POWER: 4.000000 mW, SWEEP TIME = 1.0 min

Molecular weight marker: 700 [0025] In a nanocolloid solution containing platinum and gold, the superoxide-on residual rate when the content of gold is varied is shown in Fig. 1 (chitosan / platinum / gold nanocolloid solution) and Fig. 2 ( Pectin / platinum 'gold nanocolloid solution). In any of the nanocolloid solutions, high superoxide-on erasing ability was confirmed even when the gold content was about 25 to 50%.

Figures 3 and 4 show the results when the amounts of chitosan and bectin were changed, respectively. The maximum activity was obtained at about 0.01% by weight for chitosan and about 0.01-0.025% by weight for pectin.

[0026] Example 8

Using the Pyotinyi reagent (Piothinilane Yon kit (Sulfo-OSu), manufactured by Dojin University), chitosan's pyotinyi and piotiny rate were measured. The resulting chitosan had a piotination rate of 0.02 to 0.1 (mol / mol). Using this piotinchichitosan, a platinum / gold nanocolloid solution was prepared in the same manner as in Example 3. Fig. 5 shows the results of measurement of the residual ratio of superoxide on the obtained pyotinchitosan / platinum / gold nanocolloid solution. Even when using chitosan with pyotiny, the ability to eliminate superoxide two ions was maintained.

[0027] Example 9 (Comparative example)

22.6 ml of distilled water was placed in a 100 ml two-necked eggplant bottom flask connected to a water cooling tube and a three-way cock, and chloroplatinic acid crystals (H PtCl · 6Η 0: Reagent manufactured by Wako Pure Chemical Industries, Ltd.) were distilled.

2 6 2

2 ml of a salt / platinic acid aqueous solution dissolved in water and adjusted to a concentration of 16.6 mM was added, stirred with a stirrer chip, and heated until reflux occurred. After refluxing, trisodium citrate crystals (Wako Pure Chemical Industries reagent) were dissolved in distilled water, and 8.6 ml of an aqueous citrate solution adjusted to a concentration of 38.8 mM was added and refluxed for 30 minutes. Measuring the UV-Vis spectrum of the reaction solution, the platinum ion peak disappeared, the absorption saturation due to the scattering characteristic of the metal solid was confirmed, the reduction reaction was confirmed, and the sample solution was obtained by cooling. .

[0028] Example 10:

22.6 ml of distilled water was placed in a 100 ml two-necked eggplant bottom flask connected to a water cooling tube and a three-way cock, and chloroplatinic acid crystals (H PtCl · 6Η 0: Reagent manufactured by Wako Pure Chemical Industries, Ltd.) were distilled. 2 ml of a salt / platinic acid aqueous solution dissolved in water and adjusted to a concentration of 16.6 mM was added, stirred with a stirrer chip, and heated until reflux occurred. After refluxing, trisodium citrate crystals (Wako Pure Chemical Industries reagent) were dissolved in distilled water, and 8.6 ml of an aqueous citrate solution adjusted to a concentration of 38.8 mM was added and refluxed for 30 minutes. By measuring the UV-Vis spectrum of the reaction solution, the platinum ion peak disappeared, and the saturation of absorption due to the scattering characteristic of metal solids was confirmed, confirming that the reduction reaction was complete. After cooling to room temperature, dissolve pectin (UNIPECTINE AYD30, a reagent manufactured by Dutec Foods Co., Ltd.) in distilled water over 1 hour, add 10 ml of pectin solution adjusted to a concentration of 1.98 g / L, Stir for 1 hour. Thereafter, the solvent was removed with an evaporator and then redispersed with 33.2 ml of distilled water to obtain a sample solution.

[0029] Example 11

Add 43.8 ml of distilled water to a 100 ml two-necked eggplant bottom flask connected with a water cooling tube and a three-way cock, and add chloroplatinic acid crystals (H PtCl 6Η Η: Reagents manufactured by Wako Pure Chemical Industries, Ltd.)

2 6 2

4 ml of a salt / platinic acid aqueous solution prepared at a concentration of 16.6 mM was added, stirred with a stirrer chip, and heated until reflux occurred. After refluxing, trisodium citrate crystals (Wako Pure Chemical Industries reagent) were dissolved in distilled water, and 8.6 ml of a citrate aqueous solution adjusted to a concentration of 77.2 mM was added and refluxed for 30 minutes. By measuring the UV-Vis spectrum of the reaction solution, the platinum ion peak disappeared, and the saturation of absorption due to the scattering characteristic of metal solids was confirmed, confirming the completion of the reduction reaction. After cooling to room temperature, dissolve pectin (UNIPECTINE AYD30, reagent manufactured by Nytec Foods Co., Ltd.) in distilled water over 1 hour, and adjust the concentration to 3.96 g / L. A sample solution was obtained by stirring for 1 hour.

[0030] Example 12

The difference in stability in hard water was examined for the sample solutions of Example 9 (no pectin, comparative example) and Example 10. Commercially available Evian (500 ml, Sodium 2.5 mg (0.22 mM), Calcium 39 mg (1.95 mM), Magnesium 12 mg (l mM) in hardness 291 degree medium hard water, pH 7.2) was used as hard water. . When the sample of Example 9 was diluted 10 times with hard water and observed one day later, precipitation occurred. On the other hand, when the sample of Example 10 was diluted 5 times and observed one day later, it was uniformly dispersed.

[0031] Example 13 The pH stability was examined using the sample of Example 10 (CP-PT) and platinum nanocolloid (PAA-Pt) using polyacrylic acid. Using a spectrophotometer (Amersham Ultrospec 6300 pro), measure the extinction rate of 400 M hydrogen peroxide by hydrogen peroxide spectral absorption (210 nm), and calculate the activity of platinum nanocolloid from the remaining absorbance did. The result is shown in FIG. From this result, it can be seen that, compared with the conventional nanocolloid, the platinum nanocolloid of Example 10 has significantly less influence on the activity due to pH fluctuation.

Industrial applicability

The noble metal nanocolloid solution contained in the superoxide-on scavenger of the present invention retains high reaction efficiency as a noble metal catalyst, and is excellent in intracellular uptake of noble metal nanoparticles. Therefore, the superoxide-on scavenger of the present invention is useful as a scavenger having extremely high activity. In addition to the active pharmaceutical ingredients that have no unpleasant odor, the erasing agent of the present invention has extremely desirable properties when added to beverages or foods.

Claims

The scope of the claims

[1] A superoxide vanishing scavenger comprising a noble metal nanocolloid solution containing noble metal nanoparticles and a natural product-derived polysaccharide.

[2] The superoxide anion scavenger according to claim 1, wherein the natural product-derived polysaccharide is chitosan, pectin, or a mixture thereof.

[3] The superoxide-on eraser according to claim 1 or 2, wherein the noble metal contains two kinds of noble metals consisting of platinum and gold.

[4] The superoxide-on elimination according to claim 3, wherein the ratio of platinum and gold is about 1: 1, and the content of chitosan is about 0.01% by weight with respect to the total weight of the noble metal nanocolloid solution. Agent.

5. The superoxide solution according to claim 3, wherein the ratio of platinum and gold is about 1: 1, and the content of pectin is about 0.01 to 0.025% by weight based on the total weight of the noble metal nanocolloid solution. On eraser.

[6] The superoxide-on scavenger according to claim 1, wherein 90% or more of the noble metal nanoparticles have a particle size distributed in the range of 0.1 nm to 10 nm.