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WO2004037019A1 - Metal compositions capable of removing active oxygen - Google Patents

Metal compositions capable of removing active oxygen Download PDF

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Publication number
WO2004037019A1
WO2004037019A1 PCT/JP2002/011145 JP0211145W WO2004037019A1 WO 2004037019 A1 WO2004037019 A1 WO 2004037019A1 JP 0211145 W JP0211145 W JP 0211145W WO 2004037019 A1 WO2004037019 A1 WO 2004037019A1
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Prior art keywords
active oxygen
gold
platinum
oxygen radical
foil
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PCT/JP2002/011145
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French (fr)
Japanese (ja)
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Kazuyoshi Okubo
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Takaoka Shoji Inc.
Motomura, Michiyo
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Application filed by Takaoka Shoji Inc., Motomura, Michiyo filed Critical Takaoka Shoji Inc.
Priority to AU2002343768A priority Critical patent/AU2002343768A1/en
Priority to PCT/JP2002/011145 priority patent/WO2004037019A1/en
Publication of WO2004037019A1 publication Critical patent/WO2004037019A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00Preservation of foods or foodstuffs, in general
    • A23B2/70Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/708Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23B2/712Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23B2/717Oxygen absorbent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P39/00General protective or antinoxious agents
    • A61P39/06Free radical scavengers or antioxidants

Definitions

  • the present invention relates to a metal composition having an ability to scavenge reactive oxygen radicals (Reactive Oxygen Radica1).
  • Background art Reactive Oxygen Radica1.
  • Active oxygen radicals also called simply active oxygen or free radicals, are reactive atoms and molecules with unstable unpaired electrons.
  • reactive oxygen radicals In general, super O key side (- 0 2 -), hydroxy radicals (HO *), hydrogen peroxide (H 2 0 2), 4 kinds of singlet oxygen 0 2) is referred to as reactive oxygen radicals.
  • hydroperoxy radicals (HOO *), peroxy radicals (L 00 *), alkoxy radicals (LO *) and the like are also broadly called active oxygen species and radical species.
  • active oxygen radicals are produced secondary and tertiary from active oxygen radicals.
  • active oxygen radicals which increase at an accelerated rate, cause damage to cells and DNA, peroxidation of lipids, and are involved in many diseases.
  • active oxygen radical scavengers have two aspects: elimination of active oxygen and generation of active oxygen.
  • the active oxygen radical scavenger which is a hydrogen (H *) donor, is converted into an active oxygen radical such as 0 *, HOOH, HO 0 *, and HO * (HOOH in the above equation). It donates two electrons (e-one) and reduces by two protons (H +) to eliminate active oxygen radicals.
  • the normal oxygen molecule O 2 two electrons (e-), donate two protons (H +), thereby generating an active oxygen Also involved in the process.
  • active oxygen radical scavengers and media such as aldehydes, amino acids, and peronic acid (acidic saccharides), which have poor direct working ability to process active oxygen radicals alone, are present at the same time. It was revealed that the active oxygen radical scavenger was superior to the active oxygen radical scavenger in eliminating the active oxygen than the active oxygen radical scavenger alone. In addition, it was revealed that there was a combination of active oxygen radical scavenger and mediae in the reaction to eliminate active oxygen radicals.
  • active oxygen radical X hereinafter sometimes simply referred to as “X” in the present specification
  • active oxygen radical scavenger Y hereinafter referred to as the “donor”
  • Y active oxygen radical scavenger
  • k Constant reflecting the active oxygen radical processing ability mainly by the combination of Y and Z
  • test substance if a faint luminescence phenomenon can be observed in the test substance under the coexistence of X and Y, it can be recognized that the test substance is a medium-Z. In addition, if a weak emission phenomenon can be observed in the test substance under the coexistence of X and Z, the test substance can be recognized as the active oxygen radical scavenger Y.
  • test substance is a substance consisting of the active oxygen radical X and the media Zi.
  • test substance is a substance consisting of the active oxygen radical X and the active oxygen radical force ranger Y. Can be.
  • the phenomenon of the weak light emission (hereinafter, sometimes referred to as “XYZ-based weak light emission” in the present specification) is a basic phenomenon in an oxygen environment, and is a basic and universal phenomenon that occurs near us. This phenomenon is based on the elimination of the active oxygen radical X by converting it into light energy.
  • works as a hydrogen ( ⁇ *) donor and ⁇ works as a mediator.
  • can be said to be a second scavenger because even if the activity of ⁇ , called a scavenger, is high, light energy cannot be released without the presence of ⁇ .
  • the world of media in the ⁇ -based active oxygen-eliminated luminescence is a completely unknown world with no concept.
  • the skin, digestive organs, respiratory organs, heart, blood vessels, eyes, brain, bones, and genitalia of the body are all ⁇ , and play an important role as a mediator of hydrogen in active oxygen scavenging luminescence. Disclosure of the invention
  • the inventor of the present application has analyzed the components of various substances having the ability as a media, and as a result of diligent research, found that gold, platinum, silver, and copper have the ability as a media. After elucidation, the present invention was completed.
  • the metal composition having the active oxygen scavenging ability proposed by the present invention is made of one or more of gold, platinum, silver, and copper.
  • the metal composition of the present invention is 24 gold, 23.9 gold, 23.74 gold, 23.44 gold, 23.21 gold, 22.99 gold, 22.66 gold, 21.68 gold, 18.12 gold , 14.12 gold.
  • Table 1 shows the gold, silver and copper content ratios. Table 1 Content of gold, silver and copper
  • the shape of gold, platinum, silver, and copper is not particularly limited, but is preferably foil, flake, powder, or granule because the larger the surface area, the higher the capacity of the media becomes. However, if the particle size is reduced, the surface area increases, but in consideration of the cost, foil or flake is more preferable.
  • the thickness should be about 0.1 to 0.3 zm, which is the intermediate product of foil or about 0.1 to 0.3 zm obtained by further hammering the supernatant. I like it.
  • the content ratio by weight of gold to platinum is preferably 0.01 to 100 with respect to platinum 1.
  • the weight ratio of gold to platinum if the amount of gold is less than 0.01 with respect to platinum 1, it is not preferable because the effect of gold is hardly observed, and conversely, it exceeds 100. Because the effect of platinum is not produced, it is unfavorable.
  • the active oxygen-eliminated luminescence as Z by XY was observed, but the active oxygen-eliminated luminescence as Y by XZ, the active oxygen-eliminated luminescence as XZ by Y, and the XY as XY by Z. No active oxygen-quenched luminescence was observed. Therefore, the gold leaf is recognized as the medial oxygen Z, but it is not the active oxygen radical scavenger Y, but the active oxygen radical X and the media oxygen Z, but not the active oxygen radical X. It was found that it was not a substance consisting of the active oxygen radical scavenger Y.
  • Example 2 Flaky 24 gold foil, flaky 23.9 gold foil, flaky 18.12 gold foil, flaky 14.12 gold foil, flaky 100% platinum foil, flaky 100% silver foil, flaky 100% The active oxygen-eliminated luminescence as Z by XY was measured for each of the copper foil and the flaky aluminum foil.
  • Petri dish 5 is flaked 24 gold leaf
  • Petri dish 6 is flaked 23.9 gold leaf
  • Petri dish 7 is flaked 18.12 gold foil
  • Petri dish 8 is flaked 14.12 gold foil
  • Petri dish 9 is flaked 100% platinum foil
  • Petri dish 10 is flaked 1 ⁇ 0% silver foil
  • the Petri dish 11 was a flaky 100% copper foil
  • the Petri dish 12 was a flaky aluminum foil.
  • the faint emission of the dish 5-12 is detected by the CCD camera performs Fuotonkau down computing, further from the light emission luminance displayed by performing the image processing, the brightness of the active oxygen scavenging emission as Z by XY (cd / m 2 ).
  • the metal composition of the present invention has a capability as a media, and has excellent active oxygen scavenging ability, and is therefore useful for maintaining and recovering human health and physical condition. Therefore, the metal composition of the present invention is highly versatile and is expected to be widely used as a raw material for cosmetics, pharmaceuticals, health foods and general foods.

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Abstract

It is intended to provide metal compositions having capability as a substance Z, which is scarcely capable of removing active oxygen radical by itself but promotes the effect of removing active oxygen radical in case of coexisting with an active oxygen radical scavenger, and having high capability of removing active oxygen. The above object is achieved by providing metal compositions capable of removing active oxygen characterized by comprising one or more metals selected from among gold, platinum, silver and copper. These metal compositions are widely applicable products which are expected as being usable for various purposes as materials for cosmetics, drugs, health foods and common foods.

Description

活性酸素消去能を有する金属組成物 技術分野 Metal composition having active oxygen scavenging ability

この発明は、 活性酸素ラジカル (React ive Oxygen Radi c a 1) を消去する能力を有する金属組成物に関する。 背景技術  The present invention relates to a metal composition having an ability to scavenge reactive oxygen radicals (Reactive Oxygen Radica1). Background art

活性酸素ラジカルは、 単に活性酸素あるいはフリーラジカルとも称され、 不安 定な不対電子を持つ反応性に富んだ原子や分子であり、 更に 1電子を取り込むか Active oxygen radicals, also called simply active oxygen or free radicals, are reactive atoms and molecules with unstable unpaired electrons.

、 あるいは逆に与えることにより安定性を保とうとするものである。 一般には、 スーパーォキサイド ( · 02— ) 、 ヒドロキシラジカル (HO*)、 過酸化水素 ( H202)、 一重項酸素 02) の 4種が活性酸素ラジカルと呼ばれている。 前記 4種の他に、 ヒドロペルォキシラジカル (HOO*)、 ペルォキシラジカル (L 00*)、 アルコキシラジカル (LO*) なども広い意味で活性酸素種やラジカル 種と呼ばれている。 , Or vice versa, to maintain stability. In general, super O key side (- 0 2 -), hydroxy radicals (HO *), hydrogen peroxide (H 2 0 2), 4 kinds of singlet oxygen 0 2) is referred to as reactive oxygen radicals. In addition to the above four types, hydroperoxy radicals (HOO *), peroxy radicals (L 00 *), alkoxy radicals (LO *) and the like are also broadly called active oxygen species and radical species.

活性酸素ラジカルからは、 新たな活性酸素ラジカルが、 二次的、 三次的に産生 される。 そして、 このようにして加速度的に増加する活性酸素ラジカルは、 細胞 や DNAの損傷、 脂質の過酸化等を引き起こして多くの疾病に関与することが近 年明らかにされている。  New active oxygen radicals are produced secondary and tertiary from active oxygen radicals. In recent years, it has been clarified that active oxygen radicals, which increase at an accelerated rate, cause damage to cells and DNA, peroxidation of lipids, and are involved in many diseases.

この活性酸素ラジカルを除去する、 いわゆる活性酸素ラジカルスカベンジャー 成分に関しては、 各種のフラボノィド類及びこの関連成分 (カテキン、 ケルセチ ン、 ケンフエ口一ル、 ミリセチン、 ルチン、 アントシァニン、 ポリフエノール、 他) やサポニン類など、 食素材に由来する天然成分の研究が進められている。 本願発明者は、 活性酸素ラジカルの消失反応を簡便かつ精度高く分析できる方 法の開発に取り組んできた。 この方法は、 活性酸素ラジカルの消失時に発光する フオトン放出の高感度測定に基づくものである。 これは、 本願の発明者が共同発 明者となっている特許出願 (日本 特閧平 9— 241637号公報) 中において 紹介されている。 Regarding the so-called active oxygen radical scavenger component which removes this active oxygen radical, various flavonoids and their related components (catechin, quercetin, kenfelu, myricetin, rutin, anthocyanin, polyphenol, etc.) and saponins Research on natural ingredients derived from food materials is underway. The inventor of the present application has been working on the development of a method that can easily and accurately analyze a reaction for eliminating active oxygen radicals. This method is based on a sensitive measurement of photon emission, which emits light when the active oxygen radicals disappear. This is due to the fact that the inventor of the present application is a co-inventor in a patent application (Japanese Patent Publication No. 9-241637). Has been introduced.

この日本 特開平 9一 241637号公報においても説明されているように、 活性酸素ラジカルスカベンジャーには、 活性酸素の消去と、 活性酸素の発生とい う二面性が存在している。  As described also in Japanese Patent Application Laid-Open No. Hei 9-1241637, active oxygen radical scavengers have two aspects: elimination of active oxygen and generation of active oxygen.

これを式で説明すると下記のようになる。  This can be described by the following equation.

e_ e-ヽ 2H+ e- e -、 2 H+ e_ e- ヽ 2H + e- e-, 2 H +

302 → 02*- → HOOH → HO* + HO_ + 2H20 (活性酸素の発生) (活性酸素の消去) 3 0 2 → 0 2 *-→ HOOH → HO * + HO_ + 2H 2 0 (Generation of active oxygen) (Erase of active oxygen)

前記の式は、 活性酸素ラジカルス力べンジャ一が活性酸素ラジカルを消去する プロセスを説明するものである。 ハイ ドロジェン (H*) ドナ一である活性酸素 ラジカルスカベンジャーは、 式の後半に示されるように、 0*、 HOOH、 HO 0*、 HO*などの活性酸素ラジカル (前記の式では HOOH) に、 2個の電子 ( e一) の供与と、 2個のプロトン (H+) による還元を行って活性酸素ラジカルの 消去を行うものである。 しかし、 前記の式の前半にあるように、 同時に、 通常の 酸素分子 02) に、 2個の電子 (e— ) 、 2個のプロトン (H+) を供与し、 活 性酸素を発生させるというプロセスにも関与している。 The above equation describes the process by which the active oxygen radical scavenger removes active oxygen radicals. As shown in the second half of the equation, the active oxygen radical scavenger, which is a hydrogen (H *) donor, is converted into an active oxygen radical such as 0 *, HOOH, HO 0 *, and HO * (HOOH in the above equation). It donates two electrons (e-one) and reduces by two protons (H +) to eliminate active oxygen radicals. However, as in the first half of the equation, that at the same time, the normal oxygen molecule O 2), two electrons (e-), donate two protons (H +), thereby generating an active oxygen Also involved in the process.

また、 日本 特閧平 9—241637号公報においても説明されているように 、 本願発明者は、 単独では自ら活性酸素ラジカルを消去する能力に乏しいが、 活 性酸素ラジカルスカベンジャーと共に存在することによって、 活性酸素ラジカル を消去する作用を促進させる性質を有する物質 (以下、 本明細書において、 この 物質を 「メディエー夕一」 ということがある。 ) が存在することを発見した。 すなわち、 活性酸素ラジカルスカベンジャーと、 単独で活性酸素ラジカルを処 理する直接作業能力に乏しい、 アルデヒドやアミノ酸、 ゥロン酸 (酸性糖類) な どのメデイエ一夕一が同時に存在している場合の方が、 活性酸素ラジカルス力べ ンジャー単独の場合よりも、 活性酸素ラジカルスカベンジャーによる活性酸素消 去作用に優れていることを明らかにした。 また、 活性酸素ラジカルの消失反応に おいて、 活性酸素ラジカルスカベンジャーとメディェ一夕一の組み合わせが存在 することも解明した。  In addition, as described in Japanese Patent Publication No. 9-241637, the present inventor alone has a poor ability to scavenge active oxygen radicals by itself, but by being present together with an active oxygen radical scavenger, It has been discovered that there is a substance having a property of promoting the action of eliminating active oxygen radicals (hereinafter, this substance may be referred to as “media agent” in the present specification). In other words, when active oxygen radical scavengers and media such as aldehydes, amino acids, and peronic acid (acidic saccharides), which have poor direct working ability to process active oxygen radicals alone, are present at the same time, It was revealed that the active oxygen radical scavenger was superior to the active oxygen radical scavenger in eliminating the active oxygen than the active oxygen radical scavenger alone. In addition, it was revealed that there was a combination of active oxygen radical scavenger and mediae in the reaction to eliminate active oxygen radicals.

更に、 本願の発明者は、 大豆サポニンの構造解明の過程で、 活性酸素ラジカル X (以下、 本明細書において、 単に 「X」 ということがある。 ) と活性酸素ラジ カルに電子とプロトン、 即ち水素を供与するドナ一である活性酸素ラジカルスカ ベンジャ一 Y (以下、 本明細書において、 単に 「Y」 ということがある。 ) の併 存下に、 ある種の物質が加わると、 Xの消去時に微弱発光が起こる現象を発見し た。 Furthermore, the inventor of the present application discovered that active oxygen radical X (hereinafter sometimes simply referred to as “X” in the present specification) and an active oxygen radical scavenger Y (hereinafter referred to as the “donor”) that donates electrons and protons, that is, hydrogen, to the active oxygen radical. In the book, it is sometimes referred to simply as “Y.”), and when a certain substance was added, a weak light emission occurred when X was erased.

そして、 生体には、 X、 Υ及び Υのメデイエ一夕一となる Ζの三者が揃って初 めて可能になる活性酸素消去系が存在し、 この消去系では、 励起状態にある活性 酸素のエネルギーは光として放出されているという仮説を立て、 活性酸素が消去 される瞬間を微弱発光として、 C C Dカメラで可視的に捉えた。  In addition, there is an active oxygen scavenging system in the living body, which is only possible when all three of X, Υ, and メ are the mediators of X, 、, and 消去. Based on the hypothesis that the energy is released as light, the moment when active oxygen is erased is considered as faint light emission and visually captured by a CCD camera.

その後、 メデイエ一夕一 Z (以下、 本明細書において、 単に 「Z」 ということ がある。 ) の濃度を固定して X及び Yの濃度を変えながら微弱発光強度を測定す ると、 Xの濃度と微弱発光強度は正比例することが示された。 Xの濃度を固定し て Y及び Zの濃度を変えた場合や Yの濃度を固定して X及び Zの濃度を変えた場 合においても、 同様の結果が得られた。  After that, when the weak luminescence intensity is measured while changing the concentration of X and Y while fixing the concentration of the mediae Zi (hereinafter sometimes simply referred to as “Z” in this specification), the X It was shown that the concentration and the weak luminescence intensity were directly proportional. Similar results were obtained when the concentration of X was fixed and the concentrations of Y and Z were changed, and when the concentration of Y was fixed and the concentrations of X and Z were changed.

これより、 微弱発光強度 [ P ] は、 X、 Y及び Zの濃度に依存する三次反応、 即ち、 [P ] = k [X] [Y] [ Z ] の関係で示すことができる。  Thus, the weak luminescence intensity [P] can be represented by a tertiary reaction depending on the concentrations of X, Y, and Z, that is, [P] = k [X] [Y] [Z].

[ P ] :輝度 (c d/m2 ) により数値化された微弱発光強度 (数値が大きい 程、 活性酸素消去能力が高い。 ) [P]: Weak luminescence intensity quantified by luminance (cd / m 2 ) (The higher the value, the higher the active oxygen scavenging ability.)

k:主として Yと Zの組み合わせによる活性酸素ラジカル処理能力を反映する 定数  k: Constant reflecting the active oxygen radical processing ability mainly by the combination of Y and Z

[X] :活性酸素ラジカル Xの濃度  [X]: Concentration of active oxygen radical X

[Y] :活性酸素ラジカルスカベンジャー Yの濃度  [Y]: Active oxygen radical scavenger Y concentration

[ Z ] :メデイエ一夕一 Zの濃度  [Z]: concentration of mediae one night Z

なお、 Xと Yの並存下において、 被試験物質に微弱発光の現象を認めることが できれば、 当該被試験物質は、 メデイエ一夕一 Zであると認めることができる。 また、 Xと Zの並存下において、 被試験物質に微弱発光の現象を認めることが できれば、 当該被試験物質は、 活性酸素ラジカルスカベンジャー Yであると認め ることができる。  In addition, if a faint luminescence phenomenon can be observed in the test substance under the coexistence of X and Y, it can be recognized that the test substance is a medium-Z. In addition, if a weak emission phenomenon can be observed in the test substance under the coexistence of X and Z, the test substance can be recognized as the active oxygen radical scavenger Y.

さらに、 Yの存在下において、 被試験物質に微弱発光の現象を認めることがで きれば、 当該被試験物質は、 活性酸素ラジカル Xとメデイエ一夕一 Zとからなる 物質であると認めることができる。 Furthermore, in the presence of Y, a faint luminescence phenomenon can be observed in If possible, it can be recognized that the test substance is a substance consisting of the active oxygen radical X and the media Zi.

さらにまた、 Zの存在下において、 被試験物質に微弱発光の現象を認めること ができれば、 当該被試験物質は、 活性酸素ラジカル Xと活性酸素ラジカルス力べ ンジャー Yとからなる物質であると認めることができる。  Furthermore, if a weak emission phenomenon can be observed in the test substance in the presence of Z, it is recognized that the test substance is a substance consisting of the active oxygen radical X and the active oxygen radical force ranger Y. Can be.

前記微弱発光の現象 (以下、 本明細書において、 「XYZ系微弱発光」 という ことがある。 ) は、 酸素環境下における基本的な現象で、 身近で起こる基本的で 普遍的な現象である。 この現象は、 活性酸素ラジカル Xを光エネルギーへの変換 による消去に基づき、 Υはハイドロジェン (Η*) ドナー、 Ζはそのメデイエ一 ターとして働く。 この活性酸素消去系では、 スカベンジャーと呼ばれる Υの活性 が高くても、 Ζの存在なしに光エネルギーの放出はあり得ないため、 Ζは第二の スカベンジャーとも言える。  The phenomenon of the weak light emission (hereinafter, sometimes referred to as “XYZ-based weak light emission” in the present specification) is a basic phenomenon in an oxygen environment, and is a basic and universal phenomenon that occurs near us. This phenomenon is based on the elimination of the active oxygen radical X by converting it into light energy. Υ works as a hydrogen (Η *) donor and Ζ works as a mediator. In this active oxygen scavenging system, Υ can be said to be a second scavenger because even if the activity of Υ, called a scavenger, is high, light energy cannot be released without the presence of Ζ.

ΧΥΖ系活性酸素消去発光におけるメデイエ一夕一 Ζの世界は、 これまで概念 のない全く未知の世界である。 生体の皮膚、 消化器、 呼吸器、 心臓、 血管、 眼、 脳、 骨随、 生殖器はいずれも Ζであり、 活性酸素消去発光においてハイドロジェ ンのメディエー夕一としての重要な役割を果たしている。 発明の開示  The world of media in the 消去 -based active oxygen-eliminated luminescence is a completely unknown world with no concept. The skin, digestive organs, respiratory organs, heart, blood vessels, eyes, brain, bones, and genitalia of the body are all Ζ, and play an important role as a mediator of hydrogen in active oxygen scavenging luminescence. Disclosure of the invention

本願発明者は、 メデイエ一夕一 Ζとしての能力を有する各種物質の成分を分析 し、 鋭意研究を重ねた結果、 金、 白金、 銀、 銅がメデイエ一夕一 Ζとしての能力 を有することを解明し、 本願発明を完成するに至った。  The inventor of the present application has analyzed the components of various substances having the ability as a media, and as a result of diligent research, found that gold, platinum, silver, and copper have the ability as a media. After elucidation, the present invention was completed.

すなわち、 本願発明が提案する活性酸素消去能を有する金属組成物は、 金、 白 金、 銀、 銅のいずれか一つ又は二つ以上からなるものである。  That is, the metal composition having the active oxygen scavenging ability proposed by the present invention is made of one or more of gold, platinum, silver, and copper.

金、 白金、 銀、 銅のそれそれのメデイエ一夕一 Ζとしての能力は、 銀が一番高 く、 銅、 白金、 金の順に低くなる。  The ability of gold, platinum, silver, and copper to be used as media throughout the day is highest for silver, and lower for copper, platinum, and gold in that order.

本願発明の金属組成物は、 24金、 23. 9金、 23. 74金、 23. 44金 、 23. 21金、 22. 99金、 22. 66金、 21. 68金、 18. 12金、 14. 12金のいずれかを含有するのが好ましい。 これらの金、 銀及び銅の含有 比率を表 1に示す。 表 1 金、 銀及び銅の含有比率 The metal composition of the present invention is 24 gold, 23.9 gold, 23.74 gold, 23.44 gold, 23.21 gold, 22.99 gold, 22.66 gold, 21.68 gold, 18.12 gold , 14.12 gold. Table 1 shows the gold, silver and copper content ratios. Table 1 Content of gold, silver and copper

Figure imgf000007_0001
Figure imgf000007_0001

なお、 これらは、 用途に応じて使い分けられている。 これらの中で、 2 2 . 6 6金は、 一番製造しやすく、 需要も多い。  These are used properly according to the application. Of these, 22.66 gold is the easiest to manufacture and has high demand.

金、 白金、 銀、 銅の形状は、 特に限定されないが、 表面積が大きい程、 メディ ェ一夕一 Zとしての能力が高くなるため、 箔状、 薄片状、 粉状又は粒状であるの が好ましく、 粒径を細かくすれば表面積は大きくなるが、 そのコストを考慮する と、 箔状又薄片状がより好ましい。  The shape of gold, platinum, silver, and copper is not particularly limited, but is preferably foil, flake, powder, or granule because the larger the surface area, the higher the capacity of the media becomes. However, if the particle size is reduced, the surface area increases, but in consideration of the cost, foil or flake is more preferable.

なお、 箔状又は薄片状の場合には、 その厚さは、 箔の中間製品である約 の上澄か又は前記上澄をさらに槌打ちして仕上げた約 0 . 1〜0 . 3 zmが好ま しい。  In the case of foil or flakes, the thickness should be about 0.1 to 0.3 zm, which is the intermediate product of foil or about 0.1 to 0.3 zm obtained by further hammering the supernatant. I like it.

本願発明において、 金と白金の含有重量比は、 白金 1に対し、 金が 0 . 0 1〜 1 0 0であるのが好ましい。 金と白金の含有重量比については、 白金 1に対し、 金が 0 . 0 1未満であると、 金の影響がほとんど見られないために好ましくない からであり、 逆に、 1 0 0を超えると、 白金の効果が出ないため、 好ましぐない からである。 発明を実施するための最良の形態  In the present invention, the content ratio by weight of gold to platinum is preferably 0.01 to 100 with respect to platinum 1. Regarding the weight ratio of gold to platinum, if the amount of gold is less than 0.01 with respect to platinum 1, it is not preferable because the effect of gold is hardly observed, and conversely, it exceeds 100. Because the effect of platinum is not produced, it is unfavorable. BEST MODE FOR CARRYING OUT THE INVENTION

以下、 本発明の好ましい実施形態を説明するが、 本発明はかかる実施形態に限 定されるものではなく、 特許請求の範囲の記載から把握される技術的範囲におい て種々の態様に変更可能である。  Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to such embodiments, and may be modified in various forms within the technical scope understood from the description of the claims. is there.

(実施例 1 )  (Example 1)

箱状の 2 2 . 6 6金箔について、 X Yによる Zとしての活性酸素消去発光、 X Zによる Yとしての活性酸素消去発光、 Υによる X Ζとしての活性酸素消去発光 及び Ζによる ΧΥとしての活性酸素消去発光を測定した。 Box-shaped 2.2.66 gold foil, active oxygen-eliminated luminescence as Z by XY, X The active oxygen elimination luminescence as Y by Z, the active oxygen elimination luminescence as Ζ by Υ, and the active oxygen elimination luminescence as ΧΥ by Ζ were measured.

シャーレ 1〜4を用意し、 シャーレ 1〜4のそれそれに、 1—ブ夕ノール lm 1を入れた後、 箔状の 22. 66金箔を加えた。  Prepare Petri dishes 1-4, put it in Petri dishes 1-4, put 1-butane lm 1 and add foil-like 22.66 gold leaf.

シャーレ 1 (XY Z) には、 X試薬として 2%過酸化水素水溶液 lml及び Y試薬として飽和没食子酸水溶液を 10%ァセトアルデヒド溶液に添カ卩した液体 lmlを加えた。 シャーレ 2 (XZ→Y) には、 X試薬として 2%過酸化水素水 溶液 lml及び Ζ試薬として飽和炭酸水素カリウム溶液を 10%ァセトアルデヒ ド溶液に添加した液体 lmlを加えた。 シャーレ 3 (Y^XZ) には、 Υ試薬と して飽和没食子酸水溶液を 10 %ァセトアルデヒド溶液に添加した液体 1 m 1を 加えた。 シャーレ 4 (Z XY) には、 Z試薬として飽和炭酸水素カリウム溶液 を 10%ァセトアルデヒド溶液に添カロした液体 lmlを加えた。  To Petri dish 1 (XYZ), 1 ml of a 2% aqueous hydrogen peroxide solution as an X reagent and 1 ml of a liquid obtained by adding a saturated gallic acid aqueous solution to a 10% acetoaldehyde solution as a Y reagent were added. To Petri dish 2 (XZ → Y), 1 ml of a 2% aqueous hydrogen peroxide solution as an X reagent and 1 ml of a liquid obtained by adding a saturated potassium hydrogen carbonate solution to a 10% acetoaldehyde solution as a Ζ reagent were added. To Petri dish 3 (Y ^ XZ), 1 ml of a liquid prepared by adding a saturated aqueous solution of gallic acid to a 10% acetoaldehyde solution as a reagent was added. To Petri dish 4 (ZXY), 1 ml of a liquid obtained by adding a saturated potassium bicarbonate solution to a 10% acetoaldehyde solution as a Z reagent was added.

シャーレ 1〜4内の微弱発光を CCDカメラにより検知して、 フオトンカウン ティングを行い、 さらに画像処理を行って表示した発光輝度から、 XYによる Z としての活性酸素消去発光の輝度 (cd/m2) を求めた。 By detecting weak light emission in the dish 1 to 4 by the CCD camera performs Fuotonkaun coating, further from the light emission luminance displayed by performing the image processing, the active oxygen scavenging emission as Z by XY luminance (cd / m 2) I asked.

その結果を表 2に示す。  The results are shown in Table 2.

表 2  Table 2

Figure imgf000008_0001
Figure imgf000008_0001

表 2より、 金箔については、 XYによる Zとしての活性酸素消去発光は認めら れたが、 XZによる Yとしての活性酸素消去発光、 Yによる XZとしての活性酸 素消去発光及び Zによる X Yとしての活性酸素消去発光は認められなかった。 従 つて、 金箔は、 メデイエ一夕一 Zであると認められるが、 活性酸素ラジカルスカ ベンジャ一 Yではなく、 活性酸素ラジカル Xとメデイエ一夕一 Zとからなる物質 でもなく、 活性酸素ラジカル Xと活性酸素ラジカルスカベンジャー Yとからなる 物質でもないことがわかった。  From Table 2, for the gold foil, the active oxygen-eliminated luminescence as Z by XY was observed, but the active oxygen-eliminated luminescence as Y by XZ, the active oxygen-eliminated luminescence as XZ by Y, and the XY as XY by Z. No active oxygen-quenched luminescence was observed. Therefore, the gold leaf is recognized as the medial oxygen Z, but it is not the active oxygen radical scavenger Y, but the active oxygen radical X and the media oxygen Z, but not the active oxygen radical X. It was found that it was not a substance consisting of the active oxygen radical scavenger Y.

(実施例 2 ) 薄片状の 24金箔、 薄片状の 23. 9金箔、 薄片状の 18. 12金箔、 薄片状 の 14. 12金箔、 薄片状の 100 %白金箔、 薄片状の 100 %銀箔、 薄片状の 100%銅箔、 薄片状のアルミ箔のそれそれについて、 XYによる Zとしての活 性酸素消去発光を測定した。 (Example 2) Flaky 24 gold foil, flaky 23.9 gold foil, flaky 18.12 gold foil, flaky 14.12 gold foil, flaky 100% platinum foil, flaky 100% silver foil, flaky 100% The active oxygen-eliminated luminescence as Z by XY was measured for each of the copper foil and the flaky aluminum foil.

シャーレ 5〜 12を用意し、 シャーレ 5〜 12のそれそれに 1—ブ夕ノール 1 m 1を入れた後、 シャーレ 5には薄片状の 24金箔、 シャーレ 6には薄片状の 2 3. 9金箔、 シャーレ 7には薄片状の 18. 12金箔、 シャーレ 8には薄片状の 14. 12金箔、 シャーレ 9には薄片状の 100%白金箔、 シャーレ 10には薄 片状の 1◦ 0 %銀箔、 シャーレ 11には薄片状の 100 %銅箔、 シャーレ 12に は薄片状のアルミ箔を加えた。  Prepare Petri dishes 5 ~ 12, put 1-m 1 of it in Petri dishes 5 ~ 12 and put 1m1 in them. Petri dish 5 is flaked 24 gold leaf, Petri dish 6 is flaked 23.9 gold leaf , Petri dish 7 is flaked 18.12 gold foil, Petri dish 8 is flaked 14.12 gold foil, Petri dish 9 is flaked 100% platinum foil, Petri dish 10 is flaked 1◦0% silver foil The Petri dish 11 was a flaky 100% copper foil, and the Petri dish 12 was a flaky aluminum foil.

シャーレ 5〜12のそれそれに、 X試薬として 2%過酸化水素水溶液 lml及 び Y試薬として飽和没食子酸水溶液を 10%ァセトアルデヒド溶液に添加した液 体 lmlを加えた。  To each of Petri dishes 5 to 12, 1 ml of a 2% aqueous hydrogen peroxide solution as an X reagent and 1 ml of a liquid obtained by adding a saturated gallic acid aqueous solution as a Y reagent to a 10% acetoaldehyde solution were added.

シャーレ 5〜12内の微弱発光を CCDカメラにより検知して、 フオトンカウ ンティングを行い、 さらに画像処理を行って表示した発光輝度から、 XYによる Zとしての活性酸素消去発光の輝度 ( c d/m2) を求めた。 The faint emission of the dish 5-12 is detected by the CCD camera performs Fuotonkau down computing, further from the light emission luminance displayed by performing the image processing, the brightness of the active oxygen scavenging emission as Z by XY (cd / m 2 ).

その結果を表 3に示す。  The results are shown in Table 3.

表 3  Table 3

Figure imgf000009_0001
Figure imgf000009_0001

表 3から、 本願発明の薄片状の金属組成物は、 いずれもメデイエ一夕一 Zであ ると認められ、 優れた活性酸素消去能力を持つことが確認された。  From Table 3, it was confirmed that all of the flaky metal compositions of the present invention had a mediae of overnight Z, and were confirmed to have excellent active oxygen scavenging ability.

(実施例 3)  (Example 3)

22. 66金粉、 白金粉、 銀粉、 銅粉のそれぞれについて、 XYによる Zとし ての活性酸素消去発光を測定した。 シャーレ 13〜16を用意し、 シャーレ 13〜16のそれそれに 1—プ夕ノー ル 0. 5mlを入れた後、 シャーレ 13には 22. 66金粉を 57. 2mg、 シ ヤーレ 14には白金粉 82. 6mg、 シャーレ 15には銀粉 67. lmg、 シャ ーレ 16には銅粉 51. Omgを加えた。 22. For each of the 66 gold powder, platinum powder, silver powder, and copper powder, the active oxygen-eliminated luminescence as Z by XY was measured. Prepare petri dishes 13-16, add 0.5 ml of 1-puno phenol to that of petri dishes 13-16, then add petri dish 13 with 22.66 gold powder, 57.2 mg, and petal dish 14 with platinum powder 82 6 mg, Petri dish 15 with 67.lmg of silver powder, Petri dish 16 with 51.Omg of copper powder.

シャーレ 13〜16のそれそれに、 X試薬として 3. 75%過酸化水素水溶液 0. 5 ml及び Y試薬として飽和没食子酸水溶液を 10%ァセトアルデヒド溶液 に添加した液体 0. 5 mlを加えた。  To each of Petri dishes 13 to 16, 0.5 ml of a 3.75% aqueous hydrogen peroxide solution as an X reagent and 0.5 ml of a liquid obtained by adding a saturated gallic acid aqueous solution to a 10% acetoaldehyde solution as a Y reagent were added.

シャーレ 13〜16内の微弱発光を CCDカメラにより検知して、 フオトン力 ゥンティングを行い、 さらに画像処理を行って表示した発光輝度から、 XYによ る Zとしての活性酸素消去発光の輝度 (cd/m2) を求めた。 Weak light emission in the Petri dishes 13 to 16 is detected by a CCD camera, photon force plotting is performed, and image processing is performed.From the displayed light emission luminance, the luminance of the active oxygen erased light emission as Z by XY (cd / m 2 ) was determined.

その結果を表 4に示す。  The results are shown in Table 4.

表 4  Table 4

Figure imgf000010_0001
Figure imgf000010_0001

表 4から、 本願発明の粉状の金属組成物は、 メデイエ一夕一 Zであると認めら れ、 優れた活性酸素消去能力を持つことが確認された。 産業上の利用の可能性  From Table 4, it was confirmed that the powdery metal composition of the present invention had a median composition of Z. It was confirmed that it had excellent active oxygen scavenging ability. Industrial potential

本願発明の金属組成物は、 メデイエ一夕一 Zとしての能力を有し、 優れた活性 酸素消去能力を持っため、 人の健康や体調の維持、 回復に有用なものである。 従 つて、 本願発明の金属組成物は、 化粧品、 医薬品、 健康食品及び一般食品の原料 としての広範な用途が期待される汎用性の高いものである。  INDUSTRIAL APPLICABILITY The metal composition of the present invention has a capability as a media, and has excellent active oxygen scavenging ability, and is therefore useful for maintaining and recovering human health and physical condition. Therefore, the metal composition of the present invention is highly versatile and is expected to be widely used as a raw material for cosmetics, pharmaceuticals, health foods and general foods.

Claims

請求の範囲 The scope of the claims 1. 金、 白金、 銀、 銅のいずれか一つ又は二つ以上からなることを特徴とする 活性酸素消去能を有する金属組成物。 1. A metal composition having an active oxygen scavenging ability, comprising at least one of gold, platinum, silver, and copper. 2. 24金、 23. 9金、 23. 74金、 23. 44金、 23. 21金、 22 . 99金、 22. 66金、 21. 68金、 18. 12金、 14. 12金のいずれ かを含有することを特徴とする請求の範囲第 1項に記載の活性酸素消去能を有す る金属組成物。  2.24 gold, 23.9 gold, 23.74 gold, 23.44 gold, 23.21 gold, 22.99 gold, 22.66 gold, 21.68 gold, 18.12 gold, 14.12 gold 2. The metal composition having the ability to scavenge active oxygen according to claim 1, wherein the metal composition contains any of them. 3. 形状は、 箔状、 薄片状、 粉状又は粒状であることを特徴.とする請求の範囲 第 1項又は第 2項に記載の活性酸素消去能を有する金属組成物。  3. The metal composition having an active oxygen scavenging ability according to claim 1 or 2, wherein the metal composition has a foil shape, a flake shape, a powder shape, or a granular shape. 4. 金と白金の含有重量比は、 白金 1に対し、 金が 0. .01〜100であるこ とを特徴とする請求の範囲第 1項〜第 3項のいずれか 1つの項に記載の活性酸素 消去能を有する金属組成物。  4. The method according to any one of claims 1 to 3, wherein the weight ratio of gold to platinum is 0.01 to 100 with respect to platinum 1. Active oxygen A metal composition having a scavenging ability.
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EP1598071A4 (en) * 2003-02-20 2006-04-26 Shetech Co Ltd Superoxide anion decomposing agent
EP1656840A1 (en) * 2004-11-08 2006-05-17 Fuji Photo Film Co., Ltd. Active oxygen eliminator and production method thereof

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JPH11346715A (en) * 1998-06-09 1999-12-21 Otsuka Yakuhin Kogyo Kk Production of food mixed with colloidal solution of platinum group element
WO2001036337A1 (en) * 1999-11-18 2001-05-25 Phild Co., Ltd. Production method of ultrafine gold particle-dissolved water and device therefor

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WO1991011117A2 (en) * 1990-02-05 1991-08-08 Board Of Regents, The University Of Texas System Dietary supplements comprising vitamins and minerals
JPH1160493A (en) * 1997-08-18 1999-03-02 Eiichi Tsukiji Medicine for treating/preventing disease caused by active oxygen or raw material thereof
JPH11346715A (en) * 1998-06-09 1999-12-21 Otsuka Yakuhin Kogyo Kk Production of food mixed with colloidal solution of platinum group element
WO2001036337A1 (en) * 1999-11-18 2001-05-25 Phild Co., Ltd. Production method of ultrafine gold particle-dissolved water and device therefor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1598071A4 (en) * 2003-02-20 2006-04-26 Shetech Co Ltd Superoxide anion decomposing agent
US7838043B2 (en) 2003-02-20 2010-11-23 Apt Co., Ltd Superoxide anion decomposing agent
EP1656840A1 (en) * 2004-11-08 2006-05-17 Fuji Photo Film Co., Ltd. Active oxygen eliminator and production method thereof

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