JP2006151974A - Active oxygen eliminator and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active oxygen eliminator having excellent active oxygen-eliminating activity and suitably usable through adding it to various foods/drinks and various cosmetics, and to provide a method for producing the active oxygen eliminator. <P>SOLUTION: The active oxygen eliminator comprises composite particles with platinum group element(s) bound to or included in a dendritically branched molecule, wherein it is preferable that the platinum group element be at least one embodiment selected from Pt, Pd, PtRu and PtRd. The method for producing the active oxygen eliminator involves the step of forming the composite particles by binding or including the platinum group element(s) to or in the dendritically branched molecule. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an active oxygen scavenger having an excellent active oxygen scavenging action and a method for producing the active oxygen scavenger.

Oxygen is an essential substance for life support of many living organisms, and plays various roles such as energy production in the living body. In this energy production system and other reaction systems, oxygen is converted into superoxide anion (• O ₂ ⁻ ), singlet oxygen ( ¹ O ₂ ), hydroxy anion (• OH) by the action of enzymes, ultraviolet rays, and other radiation. It is known to become active oxygen such as.
The active oxygen plays an extremely important role for a living body in terms of a bactericidal action by leukocytes, that is, an action of decomposing a foreign substance taken by phagocytes. On the other hand, when the active oxygen is excessively produced, the body tissue itself is damaged, or the production of inflammatory factors such as lipid peroxide by promoting the peroxidation of unsaturated fatty acids that form phospholipids in biological membranes. To trigger. Moreover, together with the lipid peroxide, there is a possibility that an alkoxy radical or a hydroxy radical is generated to attack a biological membrane, causing membrane damage or inactivating various useful enzymes.

  On the other hand, in the living body, examples of the enzymes that deactivate the active oxygen include superoxide dismutase (SOD), catalase, peroxidase, glutathione peroxidase, and the like. Moreover, as various vitamins which have an antioxidant effect | action, (alpha) -tocopherol (vitamin E) etc. are mentioned, for example. A normal living body is maintained by the action of these enzymes and vitamins. However, a large amount of various chemical substances that promote in vivo production of active oxygen, such as herbicides, insecticides, detergents, pharmaceuticals, and various food additives, are present in the environment surrounding modern living bodies. Due to the influence of these chemical substances, generation of active oxygen exceeding the ability of an appropriate defense mechanism by the enzymes and vitamins, and generation and accumulation of lipid peroxides occur. When the active oxygen is abnormally increased in the body, for example, various inflammations, liver disorders, kidney disorders, gastric disorders, arteriosclerosis, hemolysis, senile dementia are associated with the progression of chain reaction of peroxidation. Serious disorders such as retinopathy, pulmonary disorders, and ischemic vascular diseases may occur.

As described above, it is recognized that excessive active oxygen adversely affects the living body, and it is possible to positively impart an action of removing active oxygen to foods and drinks used daily and cosmetics applied directly to the skin. For example, foods and drinks and cosmetics containing platinum colloid having an action of removing active oxygen have been proposed (see Patent Document 1 and Patent Document 2).
However, the platinum colloids according to these proposals have a relatively large particle size and poor dispersibility, so a sufficiently satisfactory active oxygen removal action has not been obtained, and further improvement and development are desired. Currently.

JP-A-11-346715 JP 2001-122723 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide an active oxygen scavenger that has an excellent active oxygen scavenging action and is suitably used for various foods and cosmetics and a method for producing the active oxygen scavenger.

Means for solving the problems are as follows. That is,
<1> An active oxygen removing agent comprising composite particles obtained by bonding or encapsulating a platinum group element in a dendritic branched molecule.
<2> The active oxygen removing agent according to <1>, wherein the platinum group element is at least one selected from Pt, Pd, PtRu, and PtRd.
<3> The active oxygen scavenger according to any one of <1> to <2>, wherein the site of the dendritic molecule that binds or encloses the platinum group element is a metal element trapping site.
<4> The active oxygen scavenger according to any one of <1> to <3>, wherein the dendritic branched molecule is at least one selected from a dendrimer, a dendron, and a hyperbranched polymer.
<5> The active oxygen scavenger according to any one of <1> to <4>, wherein the dendritic branched molecule is contained in a part of another material.
<6> The active oxygen scavenger according to any one of <1> to <5>, wherein the molecular weight of the dendritic branched molecule is 200 or more.
<7> The active oxygen scavenger according to any one of <1> to <6>, wherein the number of generations of the dendritic branched molecule is the first generation or more.
<8> The active oxygen scavenger according to any one of <1> to <7>, wherein the composite particles have a volume average particle diameter (D50) of 0.1 to ₅₀₀ nm.
<9> A method for producing the active oxygen scavenger according to any one of <1> to <8>, wherein a composite particle is formed by bonding or encapsulating a platinum group element in a dendritic branched molecule. It is a manufacturing method of the active oxygen removal agent characterized by including a formation process.
<10> The method for producing an active oxygen remover according to <9>, wherein a platinum group element is bonded to or encapsulated in a metal element trapping site of a dendritic branched molecule.
<11> A food or drink comprising the active oxygen scavenger according to any one of <1> to <8>.
<12> A cosmetic comprising the active oxygen scavenger according to any one of <1> to <8>.

The active oxygen scavenger of the present invention contains composite particles obtained by bonding or encapsulating a platinum group element in a dendritic molecule. The active oxygen scavenger has a smaller particle size and particle size distribution than general platinum nanoparticles, and has high dispersion stability. Therefore, the active oxygen scavenger can exhibit an excellent active oxygen scavenging action and is suitably used for foods and beverages and cosmetics. be able to.
The active oxygen removal action includes at least one of a superoxide scavenging action, a singlet oxygen scavenging action, a hydrogen peroxide scavenging action, and a radical scavenging action. Among these, the singlet oxygen scavenging action is particularly preferable. preferable.

  The method for producing an active oxygen scavenger according to the present invention is a method for producing the active oxygen scavenger according to the present invention, wherein a composite particle is formed by binding or encapsulating a platinum group element in a dendritic molecule. Including a process. As a result, an active oxygen removing agent having an excellent active oxygen removing action can be efficiently produced.

  ADVANTAGE OF THE INVENTION According to this invention, the active oxygen removal agent which can solve the conventional problems, has the outstanding active oxygen removal effect | action, and is used suitably for various food and drinks and various cosmetics, and the manufacturing method of this active oxygen removal agent are provided. can do.

(Active oxygen scavenger and method for producing active oxygen scavenger)
The active oxygen scavenger of the present invention contains composite particles in which a platinum group element is bonded to or encapsulated in a dendritic molecule, and further contains other components as necessary.
The method for producing an active oxygen scavenger of the present invention includes a composite particle forming step of forming a composite particle by binding or encapsulating a platinum group element in a dendritic branched molecule, and further includes other steps as necessary. It becomes.
The active oxygen remover of the present invention is produced by the method for producing an active oxygen remover of the present invention.
Hereinafter, the details of the active oxygen scavenger of the present invention will be clarified through the description of the method for producing the active oxygen scavenger of the present invention.

<Composite particle formation step>
The composite particle forming step is a step of forming a composite particle by combining or encapsulating a platinum group element in a dendritic branched molecule.
Here, examples of the form of the bond or inclusion include chemical bond and bond by electrostatic interaction. Examples of the chemical bond include coordination bond, ionic bond, and covalent bond.

  As the composite particle forming step, a mode in which a dendritic molecule having any one of a site capable of forming a complex with a platinum group element and a site capable of binding the platinum group element by electrostatic attraction is preferably reacted.

-Dendritic molecule-
The dendritic molecule is a dendritic molecule having a substantially constant number of metal element capture sites, and preferably means a monodisperse dendritic molecule.
The dendritic molecules include not only dendrimers and dendrons that are regularly and sequentially branched from the core that is the center of branching, but also hyperbranched polymers. The dendritic molecule may be contained in a part of another material. That is, the functional group on the surface of the dendritic branched molecule may be bonded to a polymer or other material, or may be an organic molecule containing the dendritic branched molecule. For example, a molecule in which the surface of a dendrimer is bound to a polymer main chain is also included in the dendritic molecule of the present invention.

Here, the metal element capturing site (hereinafter sometimes referred to as “focal site”) can be selected as appropriate. For example, the functional group capable of binding the platinum group element and the platinum group element are electrostatically bonded. Any functional group capable of interacting with is preferred.
Examples of the type of bond in the functional group capable of binding the platinum group element include coordinate bond, chemical bond, ionic bond, and covalent bond.
Examples of the functional group capable of coordinately bonding the platinum group element include NH ₃ , RNH ₂ , N ₂ H ₄ , H ₂ O, OH ⁻ , O ⁻² , ROH, RO ⁻ , R ₂ O, and MeCOO ^{−. _{, CO 3 -2, NO 3 -}} , F -, PhNH 2, C 5 H 5 N, N 2, NO 2 -, SO 3 -2, Br -, H -, R -, C 2 H 4, C 4 ^{_{H 6, CN -, RNC,}} CO, SCN -, R 3 P, (RO) 3 P, R 3 As, R 2 S, RSH, RS -, S 2 O 3 -2, I -, and the like . In the above formula, R represents an alkyl group, Me represents a methyl group, and Ph represents a phenyl group.
Examples of the functional group capable of electrostatically interacting with the platinum group element include quaternary ammonium salts, COO ⁻ , PO ₄ ³⁻ , SO ₄ ^{2− and the} like.

The molecular weight of the dendritic molecule (especially dendrimer) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200 or more, and more preferably 1500 to 100,000. If the molecular weight is less than 200, nanoparticles may not be formed inside the dendritic branched molecule.
The generation number of the dendritic molecules is preferably 1st generation or more, more preferably 2nd generation to 10th generation. If the number of generations is less than one generation, nanoparticles may not be formed inside the dendritic molecules.

  Examples of the dendrimer include G.I. R. Newkome, C.I. N. Moorefield, F.M. "Dendrimers and Dendrons" by Fegtre (2001, published by WILEY-VCH), C.I. J. et al. Hawker et al; Chem. Soc. , Commun. , 1010 (1990), D.C. A. Tomalia et al; Angew. Chem. Int. Ed. Engl. 29, 138 (1990), C.I. J. et al. Hawker et al; Am. Chem. Soc. 112, p. 7638 (1990), J. Am. M.M. J. et al. Preferred are those described in documents such as Frechet, Science, 263, 1710 (1994).

  Specifically, as the dendrimer, those shown in the following dendrimers (1) to (8) are preferably used.

<Dendrimer (1): Amide type dendrimer>

<Dendrimer (2): Amide type dendrimer>

<Dendrimer (3): Amide type dendrimer>

<Dendrimer (4): Amide type dendrimer>

<Dendrimer (5): Propylene imine type dendrimer>

<Dendrimer (6): Propylene imine type dendrimer>

<Dendrimer (7): Propylene imine type dendrimer>

<Dendrimer (8): Methyleneimine type dendrimer>

Among the dendrimers, a method for producing a dendrimer having a trimethyleneimine skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following methods.
For example, as described in WO 93/14147 pamphlet and WO 95/02008 pamphlet, etc., a compound containing ammonia and two or more primary amino groups is used as a starting material, and acrylonitrile is used as a starting material. React to cyanoethylate. Thereafter, the nitrile group is reduced to a primary amino group using hydrogen or ammonia in the presence of an active oxygen scavenger (G1). Next, a method of synthesizing by repeating cyanoethylation and reduction to a primary amino group three times (G2 → G3 → G4) can be mentioned. In addition, G1 represents a dendrimer first generation, G2 represents a dendrimer second generation, G3 represents a dendrimer third generation, and G4 represents a dendrimer fourth generation.
In the method for producing the dendrimer, as a starting material, a compound containing at least one functional group selected from primary amino group, alcohol, phenol, thiol, thiophenol and secondary amino group in addition to ammonia is used. Also good.

Among the dendrimers, a method for producing a dendrimer having an amidoamine skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following methods. For example, as described in JP-B-7-2840, JP-B-7-57735, JP-B-7-577736, JP-A-7-267879, and JP-A-11-140180, First, a compound having a primary amino group is used as a starting material, and 2 equivalents of methyl acrylate are reacted with the amino group (Michael addition reaction) to obtain a bifunctional methyl ester compound having a nitrogen branch. Next, one of the diamine compounds having a primary amino group is reacted with the methyl ester (ester / amide exchange reaction) to leave the other primary amino group (G1). Next, a reaction with one equivalent of a diamine compound having a primary amino group is reacted with methyl ester by reaction with 2 equivalents of methyl acrylate, and the reaction to leave the other primary amino group is repeated three times (G2 → G3 → G4). ) The method of synthesizing is mentioned.
In the method for producing the dendrimer, as a starting material, a compound containing at least one functional group selected from primary amino group, alcohol, phenol, thiol, thiophenol, and secondary amino group in addition to ammonia. It may be used.

Among the dendrimers, a method for producing a dendrimer having a π-conjugated polyarylazomethine skeleton having a branched structure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following methods. For example, K.K. Yamamoto et al; Am. Chem. Soc. 123, 4414 (2001), first, a reaction product (G2) of an amino group of 4,4′-diaminobenzophenone and 2 equivalents of a ketone of benzophenone is obtained. Then, a reaction product (G3) of 4,4′-diaminobenzophenone amino group and twice the amount of G2 ketone is obtained. Further, similarly, after obtaining a reaction product (G4) of an amino group of 4,4′-diaminobenzophenone and a double amount of a ketone of G3, a compound containing two amino groups and a double amount of G4 And the like.
The dendrimer containing a π-conjugated polyarylazomethine skeleton having a branched structure is preferably a structure branched at other than an aromatic ring. The dendrimer may be a commercially available product or may be appropriately synthesized.

  As the dendron, for example, the following dendrons (1) to (4) are preferably used. Among these, in order to produce monodispersed composite particles having a uniform particle size, the dendron having a mercapto group at the focal site, that is, the dendrons of the dendrons (1) and (3) are preferable. . In this case, since one mercapto group of a plurality of focal sites captures one platinum group element, the resulting composite particles are reverse micelles, and are excellent in dispersibility in resins and the like. Furthermore, it can be easily arranged due to self-assembling properties, resulting in a sharp particle size distribution.

-Dendron (1)-

-Dendron (2)-

-Dendron (3)-

-Dendron (4)-

As a method of synthesizing the dendron, for example, when synthesizing the dendron (1), 3,5-bis [3,5-bis (benzyloxy) benzyloxy] benzyl bromide, thiourea, and a polar solvent are used. Examples of the method include mixing and stirring, adding an aqueous sodium hydroxide solution, adjusting the pH to 2 to 3 with dilute hydrochloric acid, and then extracting with ethyl acetate.
The position of the focal site in the dendron may be present in the branched chain of the dendron. In addition, the said dendron may be a commercial item and what was synthesize | combined suitably.

  As the hyperbranched polymer, for example, the following hyperbranched polymers (1) to (2) are preferably used.

<Hyperbranched polymer (1)>

<Hyperbranched polymer (2)>

Examples of the method for producing the hyperbranched polymer include M.I. As described in Suzuki et al; Macromolecules, 25, 7071 (1992), 31, 1716 (1998), by a ring-opening polymerization of a cyclic compound using a primary amine as a nucleophilic component and a palladium catalyst. Examples include synthesis methods.
The hyperbranched polymer may be a commercially available product or may be appropriately synthesized.

It is preferable that the dendritic molecule (particularly dendrimer) does not have a site that interacts with the platinum group element other than the focal site. That is, as in the previous dendrimers (1) to (8), those having a platinum group element focal site inside and having no surface interacting with the platinum group element on the surface can be used as it is. In addition to the focal site, those having many sites that interact with the platinum group element have a smaller interaction ability (coordination ability) than the site that interacts with the platinum group element other than the focal site. It is preferable to introduce a substituent so as not to have a site that interacts with a platinum group element other than the focal site. That is, the interaction force between the focal site in the dendritic molecule and the platinum group element is greater than the interaction force between the site other than the focal site in the dendritic molecule and the platinum group element. preferable. The substituent having a small interaction ability is preferably larger than the surface region of the dendritic molecule. For example, the branching end of a dendritic branched molecule is converted to an amino group containing a hydrogen atom and reacted with methyl vinyl ketone, phenyl vinyl ketone, methyl vinyl sulfone, phenyl vinyl sulfone, etc., to introduce a substituent having a low interaction force. To do.
Examples of the substituent having a small coordination ability include a phenyl group, a benzyl group, a substituted or unsubstituted alkyl group, and the like.

  When a hard substituent having a benzene ring such as a phenyl group or a benzyl group is introduced on the surface of the dendrimer, the dendrimer and the particle-containing dendrimer have high heat resistance, rigidity, and light collecting ability. Therefore, it can be suitably used for applications that require such performance.

-Platinum group element-
Examples of the platinum group element include ruthenium (Ru), rhodium (Rd), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), and alloys thereof. Among these, Pt, Pd, PtRu, and PtRd are particularly preferable.

As the addition amount of the platinum group element, when the dendritic molecule has a focal site in the molecular chain, the number of platinum group elements to be added is equal to or less than the number of focal sites of the dendritic molecule. It is preferable. Thereby, it is possible to efficiently form particles without an operation of removing excess platinum group elements not captured by the dendritic branched molecules.
Further, when the number of platinum group elements to be added exceeds the number of focal sites of the dendritic branched molecule, after removing excess platinum group elements not captured by the focal site of the dendritic branched molecule, It is preferable to convert the platinum group element trapped in the particles into particles. In this case, it is preferable in that seed particles composed of particles corresponding to the focal site can be formed, and particles having a substantially uniform particle size and composition can be formed. In addition, even when the number of platinum group elements to be added is equal to the number of focal sites of the dendritic molecule, it is preferable in that particles having substantially uniform particle size and composition can be formed.

  As a means for trapping platinum group elements in all of the focal sites of the dendritic molecule, when the dendritic molecule has a focal site during branching, (1) an equivalent amount to the focal site in the dendritic molecule And (2) a method of adding an excess platinum group element from the focal site in the dendritic molecule and removing (for example, dialysis) the excess platinum group element.

  In addition to the mode in which one platinum group element captures one platinum group element, a mode in which two or more focal sites capture one platinum group element may be employed.

As a method for producing the active oxygen remover, in the composite particle forming step, when mixing a liquid containing a dendritic molecule and a liquid containing a platinum group element, both liquids are dropped simultaneously and mixed. From the viewpoint of forming uniform composite particles having a small particle size distribution. In this case, it is preferable that the liquid containing the dendritic molecule and the liquid containing a platinum group element are mixed in approximately equal amounts. Moreover, it is preferable to mix the liquid containing the said dendritic molecule and the liquid containing a platinum group element, heating, and heating temperature is 15-90 degreeC normally.
There is no restriction | limiting in particular as a container which puts the said both liquids and is dripped, According to the objective, it can select suitably, For example, a combination of a syringe, a syringe, and a tube, a Y-shaped microtube, a microreactor, etc. Is mentioned.
The liquid feeding of the both liquids includes manual, syringe pump, other means, etc., and it is preferable to feed both liquids by at least one of continuous and intermittent methods. Is particularly preferable since the mixing efficiency is improved.

  Here, an example of a method of mixing a liquid containing a dendritic molecule and a liquid containing a platinum group element will be specifically described. For example, as shown in FIG. 1, a solution containing dendrimer is put into syringe A, a solution containing a platinum group element is put into syringe B, both syringes are pushed out at the same time, and simultaneously dropped into a beaker at a constant speed and stirred. . The liquid feeding can be performed manually, by a syringe pump, or the like, and the dropping rate is usually 0.05 to 10 ml / min. In addition, in FIG. 1, you may make it attach a tube to the front-end | tip of a syringe and heat this tube.

Further, as shown in FIG. 2, using a tube assembled in a Y-shaped flow path, a liquid containing a dendrimer is fed from the A direction, and a liquid containing a platinum group element is fed from the B direction, and simultaneously in a beaker. Drip at a constant speed and stir. The liquid feeding can be performed manually, with a syringe pump, or the like. The liquid feeding from the A and B directions may be either continuous or intermittent, and the liquid containing the dendrimer and the liquid containing the platinum group element can be obtained by intermittently feeding the A direction and the B direction. Efficient and uniform mixing is possible.
Note that the Y-shaped flow path in FIG. 2 may be formed by forming a flow path on a substrate of metal, glass, silicon, or the like other than the tube. You may heat the mixing part-C of A and B in a Y-shaped channel. As for heating temperature, 15-90 degreeC is preferable normally. The dropping rate is usually preferably 0.05 to 10 ml / min.

  The composite particles produced by the method for producing an active oxygen scavenger of the present invention are monodisperse particles having a constant particle size and a substantially uniform composition between the particles. There is no restriction | limiting in particular, According to the objective, it can select suitably, 0.1 nm-500 nm are preferable, 0.3 nm-100 nm are more preferable, 0.3 nm-10 nm are still more preferable. The particle size means the diameter when the particle shape is spherical, and the long side when the particle shape is rod-shaped. Further, the particle size distribution of the particles can be narrowed to 0 to 200 nm.

  The active oxygen scavenger of the present invention contains the composite particles, and has a small particle size and particle size distribution and high dispersion stability. Therefore, the active oxygen scavenger is used in various forms such as powder, aqueous solution and colloidal solution. However, it is particularly suitably used for the following foods and drinks and cosmetics.

(Food)
The food and drink contains the active oxygen scavenger of the present invention, and further contains other components appropriately selected as necessary.
The foods and drinks are those that are less likely to harm human health and are taken by oral or gastrointestinal administration in normal social life, such as foods, pharmaceuticals, quasi drugs in administrative divisions, etc. It is not limited to this category, and means, for example, a wide range of foods that are orally ingested, including general foods, health foods, health functional foods, quasi drugs, and pharmaceuticals.

  There is no restriction | limiting in particular as said food-drinks, Although it can select suitably according to the objective, For example, drinks, such as a soft drink, a carbonated drink, a nutrition drink, a fruit drink, a lactic acid drink; Ice cream, ice sherbet, shaved ice Noodles such as buckwheat noodles, udon, harusame, gyoza skin, Chinese noodles, instant noodles, etc .; rice cake, candy, gum, chocolate, tablet confectionery, snack confectionery, biscuits, jelly, jam, cream, baked confectionery Confectionery such as bread; crab, salmon, clams, tuna, sardines, shrimp, skipjack, mackerel, whale, oyster, saury, squid, red sea bream, scallops, abalone, sea urchin, crabs, tocobushi, etc .; Fishery and livestock processed foods such as sausages; Dairy products such as processed milk and fermented milk; salad oil, tempura oil, margarine, mayonnaise, show Oils and processed oils such as ning, whipped cream and dressing; seasonings such as sauces and sauces; curry, stew, oyakodon, rice bowl, miscellaneous foods, Chinese rice bowl, and rice cake, tempura, eel rice cake, hayashi rice, oden, marbodorf, Retort pouch foods such as beef bowl, meat sauce, egg soup, omelet rice, dumplings, shumai, hamburg, meatballs; various forms of health and nutritional supplements; pharmaceuticals such as tablets, capsules, drinks, troches, etc. Goods. In addition, the said food / beverage is not limited to the said illustration.

As said other component, the auxiliary | assistant raw material or additive normally used in manufacturing the said food / beverage is mentioned.
The raw material or additive is not particularly limited and may be appropriately selected depending on the intended purpose.For example, glucose, fructose, sucrose, maltose, sorbitol, stevioside, rubusoside, corn syrup, lactose, citric acid, Tartaric acid, malic acid, succinic acid, lactic acid, L-ascorbic acid, dl-α-tocopherol, sodium erythorbate, glycerin, propylene glycol, glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, gum arabic , Carrageenan, casein, gelatin, pectin, agar, vitamin Bs, nicotinamide, calcium pantothenate, amino acids, calcium salts, pigments, fragrances, preservatives, and the like.

  The addition amount of the active oxygen scavenger of the present invention in the food and drink varies depending on the type of food and drink to be targeted, and cannot be specified unconditionally, but is added within a range that does not impair the original taste of the food or drink. 0.001-50 mass% is preferable normally with respect to various object food-drinks, and 0.01-20 mass% is more preferable. Moreover, in the case of the food / beverage of a granule, a tablet, or a capsule form, 0.01-100 mass% is preferable normally, and 5-100 mass% is more preferable.

(Cosmetics)
The cosmetic contains the active oxygen scavenger of the present invention, and further contains other components appropriately selected as necessary.

  The cosmetic is not particularly limited and may be appropriately selected depending on the intended purpose.For example, an ointment, cream, emulsion, lotion, pack, jelly, lip balm, lipstick, hair cream, hair liquid, bath preparation, Etc.

  The blending amount of the active oxygen scavenger with respect to the entire cosmetic varies depending on the type of the cosmetic and can be adjusted as appropriate, and is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

In the cosmetic containing the active oxygen scavenger, various main ingredients and auxiliaries usually used in the production of cosmetics and other components may be used as long as the effects of the present invention are not impaired as required. it can.
The other components are not particularly limited and include components appropriately selected according to the purpose. For example, whitening agents, astringents, bactericidal / antibacterial agents, ultraviolet absorbers, humectants, cell activators, anti-inflammatory / Examples include antiallergic agents, fats and oils, waxes, hydrocarbons, fatty acids, alcohols, esters, surfactants, fragrances, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Example 1)
-Preparation of active oxygen scavenger (composite particles)-
Using a 50 ml Erlenmeyer flask, 10.0 ml (15.0 × 10 ⁻⁵ mol) of 15 mM K ₂ [PtCl ₄ ] aqueous solution was transferred to a 20 ml dropping funnel. Add 5.0 ml of an aqueous solution of 0.5 mM dendrimer (trade name: Starburst (polyamidoamine type dendrimer (PAMAM), 4th generation, having 64 OH groups on the surface)) to another 50 ml Erlenmeyer flask. After putting, while stirring with a magnetic stirrer, the platinum ion solution was added dropwise at room temperature over 5 minutes, and then stirred at 40 ° C. for 4 hours.
For the platinum ion-dendrimer complex / water, the amount of nitrogen atoms was measured by elemental analysis (Perkin Elmer, 2400) and the amount of platinum ions was measured by atomic absorption analysis (manufactured by Hitachi, Ltd., Z5010), and the amount of platinum ions / N It was confirmed that the atomic weight ratio was 60/62.

When the UV spectrum of the obtained solution was measured, a new absorption not observed in the aqueous solution of the polyamidoamine type dendrimer and the aqueous K ₂ [PtCl ₄ ] was observed at 260 nm.
When the reaction solution was coated and dried on a washed PET base, ESCA (Electron Spectroscopic for Chemical Analysis) was measured, and a chemical shift of 73 of Pt-4f _7/2 in a K ₂ [PtCl ₄ ] aqueous solution was measured. 0.0 eV changed to 72.5 eV. It was also confirmed that 398.4 eV of the N-1s chemical shift of the polyamidoamine type dendrimer was changed to 399.3 eV.

(Example 2)
-Preparation of dendrons with mercapto groups at the focal site-
3,5-Bis [3,5-bis (benzyloxy) benzyloxy] benzoyl bromide 1.61 g (2.0 mmol), thiourea 0.18 g (2.4 mmol), and dimethyl sulfoxide (DMSO) 10 ml are mixed at room temperature. The reaction mixture was obtained by stirring overnight. To the obtained reaction mixture, 5 ml of a 10% by mass aqueous sodium hydroxide solution was added and stirred at room temperature for 1 hour. Next, the stirred solution was adjusted with diluted hydrochloric acid to have a pH of 2 to 3, and extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was distilled off to obtain 1.38 g of a dendron having a mercapto group at the focal site represented by the following formula as an oil. (Yield 92%).
The dendron having a mercapto group at the focal site was identified by measuring ¹ H-NMR spectrum using deuterated chloroform as a solvent.

-Preparation of active oxygen scavenger (composite particles)-
A solution in which 20.0 mg (58.8 mmol) of HPtCl ₄ is dissolved in 5 ml of ion-exchanged water is added to a solution in which 2.5 mg (7.4 mmol) of dendron having a mercapto group at the focal site is dissolved in 5 ml of ethyl acetate. And stirred at room temperature for 5 minutes. To this solution, a solution in which 22.8 mg (600 mmol) of NaBH ₄ was dissolved in 5 ml of ion-exchanged water was uniformly added and stirred at room temperature for 5 minutes to obtain platinum composite particles coordinated with dendron.
As a result of observing the obtained platinum composite particles with a transmission electron microscope (TEM), a space corresponding to two dendron molecules was observed between the platinum nanoparticles. From this, it was confirmed that the platinum nanoparticles were covered with dendron molecules.

(Comparative Example 1)
-Production of platinum nanocolloid (active oxygen scavenger)-
Poly (1-vinyl-2-pyrrolidone) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.147 g is placed in a 100 mL two-necked eggplant type flask connected with an Allen cooling tube and a three-way cock, and dissolved in 23 mL of distilled water. did. The solution was stirred for 10 minutes, added chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O, Wako Pure Chemical Industries, Ltd.) aqueous solution ^{(1.66 × 10 -2 mol / L} ) 2mL, further 30 Stir for minutes. The reaction system was purged with nitrogen, and 25 mL of special grade ethanol was added and refluxed at 100 ° C. for 2 hours while maintaining a nitrogen atmosphere. The UV of the reaction solution was measured, and the completion of the reduction reaction was confirmed from the disappearance of the platinum ion peak and the saturation of the peak due to the scattering characteristic of the metal solid.
Next, after distilling off the organic solvent under reduced pressure, water was added to prepare a platinum nanocolloid liquid (platinum concentration 1 mmol / L). The average particle diameter of the platinum nanocolloid in the obtained platinum nanocolloid liquid was 2.4 ± 0.7 nm.

  Next, in Examples 1 and 2, Comparative Example 1, known β-carotene, sodium azide, ascorbic acid, hypotaurine, and mannitol as active oxygen scavengers, the singlet oxygen scavenging action was confirmed as follows. The singlet oxygen removal constant was measured. The results are shown in Table 1. In Examples 1 and 2, the measurement was performed using a sample having the same platinum concentration (1 mmol / L) as Comparative Example 1.

<Measurement of singlet oxygen removal constant>
As the singlet oxygen detection device, the device described in Japanese Patent No. 3356517 was used. A 200 μmol / L aqueous solution of rose bengal was circulated in the flow cell at a rate of 20 mL / min. When this cell was irradiated with a laser having a wavelength of 514.5 nm, which is an absorption wavelength of rose bengal, light emission accompanying the transition of singlet oxygen was observed, and the emission peak was 1268 nm. Next, platinum nanocolloid liquid was added at various concentrations (platinum concentration in the range of 1 to 10 μmol / L), and the emission intensity (I) was measured. The intensity ratio (I ₀ ) / (I) between the emission intensity (I) and (I ₀ ) at each concentration is plotted against the concentration (Cq: platinum concentration), and the singlet oxygen removal constant (kq )
<Formula 1>
I ₀ / I = 1 + kq · τ · Cq
However, in Formula 1 (Stern-Volmer formula), I ₀ represents the emission intensity associated with the transition of singlet oxygen when no active oxygen scavenger is contained. I represents the emission intensity when an active oxygen scavenger is added. kq represents a reaction rate constant. τ is a constant indicating the lifetime of singlet oxygen. Cq represents the concentration of the active oxygen scavenger.

表１の結果から、実施例１及び２は、活性酸素除去剤として公知のβ−カロチン、アジ化ナトリウム、アスコルビン酸、ヒポタウリン、及びマンニトールよりも高く、比較例１の白金ナノコロイドと同レベルの優れた一重項酸素除去作用を有し、活性酸素除去剤として有用であることが認められる。

From the results of Table 1, Examples 1 and 2 are higher than the known β-carotene, sodium azide, ascorbic acid, hypotaurine, and mannitol as active oxygen scavengers, and have the same level as the platinum nanocolloid of Comparative Example 1. It is recognized that it has an excellent singlet oxygen scavenging action and is useful as an active oxygen scavenger.

(Formulation Example 1)
-Preparation of emulsion-
An emulsion having the action of removing active oxygen having the following composition was produced by a conventional method.
Active oxygen scavenger 1.0g of Example 1, jojoba oil 4.0g, placenta extract 0.1g, magnesium ascorbate 0.1g, olive oil 2.0g, squalane 2.0g, cetanol 2.0g, mono Glyceryl stearate 2.0 g, polyoxyethylene cetyl ether (20E.O.) 2.5 g, oleic acid polyoxyethylene sorbitan (20E.O.) 2.0 g, 1.3-butylene glycol 3.0 g, hinokitiol 0 .15 g, fragrance 0.15 g, and the remainder of purified water were added to make the total amount 100 g.

(Formulation Example 2)
-Preparation of cream-
A cream having the action of removing active oxygen having the following composition was produced by a conventional method.
Active oxygen scavenger 1.0g of Example 2, liquid paraffin 5.0g, white beeswax 4.0g, cetanol 3.0g, squalane 10.0g, lanolin 2.0g, arbutin 0.1g, lucinol 0.1g, Koji 0.1 g of acid, 0.1 g of conchiolin, 0.1 g of buckwheat extract, 1.0 g of stearic acid, 1.5 g of polyoxyethylene sorbitan (20E.O.) oleate, 3.0 g of glyceryl monostearate, 1.3 The remaining amount of butylene glycol 6.0 g, methyl paraoxybenzoate 0.05 g, fragrance 0.1 g, and purified water was added to make a total amount of 100 g.

(Formulation Example 3)
-Preparation of capsules-
Capsules having the following composition for removing active oxygen were produced by a conventional method.
The active oxygen scavenger of Example 1 20.0 mg, corn starch 60.0 mg, lactose 100.0 mg, calcium lactate 10.0 mg, and hydroxypropylcellulose (HPC-L) 10.0 mg were mixed by a conventional method, and No. 1 hardware Filled into gelatin capsules.

(Formulation Example 4)
-Preparation of capsules-
Capsules having the following composition for removing active oxygen were produced by a conventional method.
The active oxygen scavenger 20.0 mg of Example 2, corn starch 60.0 mg, lactose 100.0 mg, calcium lactate 10.0 mg, and hydroxypropylcellulose (HPC-L) 10.0 mg were mixed by a conventional method, and No. 1 hardware Filled into gelatin capsules.

  The active oxygen scavenger of the present invention has an excellent active oxygen scavenging action. For example, various cosmetics such as ointments, creams, emulsions, lotions, packs, jellies, lip balms, lipsticks, hair creams, hair liquids, bathing agents, etc. For example, it can be suitably used by being widely added to foods and drinks such as general foods, health foods, health functional foods, quasi drugs, and pharmaceuticals taken orally.

FIG. 1 is a schematic view showing an example of a method for simultaneously adding a liquid containing a dendritic molecule and a liquid containing a platinum group element. FIG. 2 is a schematic view showing an example of a method for simultaneously adding a liquid containing a dendritic molecule and a liquid containing a platinum group element.

Claims (10)

  An active oxygen removing agent comprising composite particles in which a platinum group element is bonded to or encapsulated in a dendritic molecule.   The active oxygen scavenger according to claim 1, wherein the platinum group element is at least one selected from Pt, Pd, PtRu, and PtRd.   The active oxygen scavenger according to any one of claims 1 to 2, wherein the site of the dendritic molecule that binds or encloses the platinum group element is a metal element capturing site.   The active oxygen scavenger according to any one of claims 1 to 3, wherein the dendritic branched molecule is at least one selected from a dendrimer, a dendron, and a hyperbranched polymer.   The active oxygen scavenger according to any one of claims 1 to 4, wherein the dendritic molecule is contained in a part of another material.   The active oxygen scavenger according to any one of claims 1 to 5, wherein the molecular weight of the dendritic molecule is 200 or more.   The active oxygen scavenger according to any one of claims 1 to 6, wherein the number of generations of the dendritic molecule is 1st generation or more. The active oxygen scavenger according to any one of claims 1 to 7, wherein the composite particles have a volume average particle diameter (D50) of 0.1 to ₅₀₀ nm.   A method for producing an active oxygen scavenger according to any one of claims 1 to 8, comprising a composite particle forming step of forming a composite particle by binding or encapsulating a platinum group element in a dendritic branched molecule. A method for producing a characteristic active oxygen scavenger. The method for producing an active oxygen removing agent according to claim 9, wherein a platinum group element is bonded to or encapsulated in a metal element capturing site of the dendritic molecule.

Images