JP4326382B2 - PVP / fullerene complex and method for producing aqueous solution thereof - Google Patents
PVP / fullerene complex and method for producing aqueous solution thereof Download PDFInfo
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 88
- 229910003472 fullerene Inorganic materials 0.000 title claims description 85
- 239000007864 aqueous solution Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 83
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 83
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 83
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000001766 physiological effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000002000 scavenging effect Effects 0.000 description 4
- 238000013319 spin trapping Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- -1 halogen aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
この出願の発明は、抗酸化活性、抗ガン性、抗菌性等の生理活性を有するものとして注目されているフラーレン類の水溶液と、水溶性のフラーレン類の新しい製造方法に関するものである。 The invention of this application relates to an aqueous solution of fullerenes that are attracting attention as having physiological activities such as antioxidant activity, anticancer activity, and antibacterial activity, and a new method for producing water-soluble fullerenes.
Ｃ６０、Ｃ７０、さらにはより高次の炭素球殻構造やチューブ構造を有するフラーレンは、その化学的修飾体や複合体、包接体等を含めたフラーレン類として、抗酸化活性、抗ガン性、抗菌性等の生理活性を有するものとして注目されつつある。 Fullerenes having C60, C70, and higher-order carbon spherical shell structures and tube structures are used as fullerenes including chemical modifications, composites, clathrates, etc., as an antioxidant activity, an anti-cancer property, It is attracting attention as having physiological activities such as antibacterial properties.
しかしながら、このようなフラーレン類を実際に使用しようとする場合、上記のような生理活性等の優れた特性を発現させるのが可能であって、しかも安定性を良好として利用可能とすることは大変に難しく、また、水溶性のものとすることや、具体的に水溶液を構成することも難しいのが実情であった。 However, when such fullerenes are actually used, it is possible to develop excellent characteristics such as physiological activity as described above, and it is very difficult to use them with good stability. In reality, it is difficult to make it water-soluble, and it is also difficult to construct an aqueous solution specifically.
このような状況において、この出願の発明者らは、フラーレン類含有の新しい抗酸化剤や外用組成物、その化粧品用材等をすでに提案し（たとえば特許文献１）、具体的にも、水溶性フラーレン類、フラーレン類の水溶液を提案している。そして、特に、生理活性の発現性と安定性の両面より、フラーレンまたはフラーレン混合物とポリビニルピロリドン（ＰＶＰ）との複合体が注目されるものとして提案している。
上記のように注目されるＰＶＰ・フラーレン複合体ではあるが、その製造についてはさらなる改善が望まれてもいた。 Although it is a PVP / fullerene complex attracting attention as described above, further improvement has been desired for its production.
それと言うのも、これまでの方法によれば、フラーレンやフラーレンの混合物の溶媒として知られているトルエン、キシレン、ベンゼン、クロロベンゼン等の芳香族炭化水素にはＰＶＰ（ポリビニルピロリドン）がほとんど溶解しないことからクロロホルム、ジクロロメタン、1,2-ジクロロエタン等のハロゲン化脂肪族炭化水素溶媒(-CHX2基を含む溶剤)を用いることで混合溶液を調製してきているため、このようなハロゲン脂肪族化炭化水素溶媒はその残留の問題や環境への負荷の問題等が懸念されていたからである。このため、ハロゲン脂肪族化炭化水素溶媒を用いることなしに、その特性の発現や安定性が良好で、安全性にも優れたＰＶＰ・フラーレン複合体、そしてその水溶液を製造することのできる方法の実現が望まれていた。 This is because PVP (polyvinylpyrrolidone) hardly dissolves in aromatic hydrocarbons such as toluene, xylene, benzene, and chlorobenzene, which are known as solvents for fullerenes and fullerene mixtures, according to conventional methods. Since mixed solutions have been prepared using halogenated aliphatic hydrocarbon solvents (solvents containing -CHX 2 groups) such as chloroform, dichloromethane, 1,2-dichloroethane, etc., such halogen aliphatic hydrocarbons This is because there are concerns about the problem of residual solvent and environmental load. Therefore, without using a halogenated aliphatic hydrocarbon solvent, a PVP / fullerene complex having excellent characteristics and stability, excellent safety, and an aqueous solution thereof can be produced. Realization was desired.
そこで、この出願の発明は、以上のような背景から、ハロゲンフリーの条件下での新しいＰＶＰ・フラーレン複合体とその水溶液の製造方法を提供することを課題としている。 Then, the invention of this application makes it a subject to provide the manufacturing method of the new PVP and fullerene complex and its aqueous solution on halogen-free conditions from the above backgrounds.
この出願の発明は、上記の課題を解決するものとして、第１には、フラーレンまたはフラーレン混合物の芳香族炭化水素溶液とポリビニルピロリドン（ＰＶＰ）のエタノール溶液とを混合し、混合溶液への水の添加と溶媒の除去の後にフラーレンまたはフラーレン混合物とポリビニルピロリドン（ＰＶＰ）との複合体の水溶液を得ることを特徴とするＰＶＰ・フラーレン複合体水溶液の製造方法を提供する。 The invention of this application is to solve the above-mentioned problems. First, an aromatic hydrocarbon solution of fullerene or a fullerene mixture and an ethanol solution of polyvinylpyrrolidone (PVP) are mixed, and water in the mixed solution is mixed. Provided is a method for producing an aqueous solution of a PVP / fullerene complex, wherein an aqueous solution of a complex of fullerene or a mixture of fullerenes and polyvinylpyrrolidone (PVP) is obtained after addition and removal of the solvent.
第２には、上記方法において、ポリビニルピロリドン（ＰＶＰ）の重量平均分子量が６，０００〜１，５００、０００の範囲であることを特徴とするＰＶＰ・フラーレン複合体水溶液の製造方法を、第３には、ポリビニルピロリドン（ＰＶＰ）のエタノール溶液におけるポリビニルピロリドン（ＰＶＰ）とエタノール（Ｅ）との重量比（ＰＶＰ／Ｅ）を０．０１〜０．５の範囲とすることを特徴とするＰＶＰ・フラーレン複合体水溶液の製造方法を、第４には、フラーレンまたはフラーレン混合物の芳香族炭化水素溶媒溶液（Ｆ・Ａ）とポリビニルピロリドンのエタノール溶液（ＰＶＰ・Ｅ）との混合に際しての重量比（Ｆ・Ａ／ＰＶＰ・Ｅ）を１．０〜３．０の範囲とすることを特徴とするＰＶＰ・フラーレン複合体の製造方法を、第５にはＰＶＰ・フラーレン複合体の濃度を５〜２０重量％の範囲とすることを特徴とするＰＶＰ・フラーレン複合体水溶液の製造方法を提供する。 Secondly, in the above method, a method for producing a PVP / fullerene complex aqueous solution, wherein the weight average molecular weight of polyvinylpyrrolidone (PVP) is in the range of 6,000 to 1,500,000, Has a weight ratio (PVP / E) of polyvinylpyrrolidone (PVP) and ethanol (E) in an ethanol solution of polyvinylpyrrolidone (PVP) in the range of 0.01 to 0.5. A fourth method for producing a fullerene complex aqueous solution is the weight ratio (F / A) when mixing an aromatic hydrocarbon solvent solution (F · A) of fullerene or a fullerene mixture with an ethanol solution (PVP · E) of polyvinylpyrrolidone. · A / PVP · E) in the range of 1.0 to 3.0, fifthly, a method for producing a PVP / fullerene composite, To provide a method of manufacturing a PVP · fullerene complex solution, characterized in that the concentration of PVP · fullerene complex ranges from 5 to 20 wt%.
第６には、上記のいずれかの発明の方法により製造したＰＶＰ・フラーレン複合体の水溶液から水を蒸発除去することを特徴とするＰＶＰ・フラーレン複合体の製造方法を提供する。 Sixth, the present invention provides a method for producing a PVP / fullerene complex, characterized by evaporating and removing water from an aqueous solution of the PVP / fullerene complex produced by the method of any of the above inventions.
そして、第７には、上記第６の発明の方法により製造したＰＶＰ・フラーレン複合体を水と混合することを特徴とするＰＶＰ・フラーレン複合体水溶液の製造方法を提供する。 Seventh, the present invention provides a method for producing a PVP / fullerene complex aqueous solution, wherein the PVP / fullerene complex produced by the method of the sixth invention is mixed with water.
上記のとおりのこの出願の発明によって、残留による人体への影響やその処分の環境負荷の増大が懸念されるハロゲン脂肪族化炭化水素溶媒を使用することなしに、ハロゲンフリーの条件下に、医薬品許容溶媒としてのエタノールを用いてＰＶＰ・フラーレン複合体とその水溶液の製造が可能とされる。そして製造されたＰＶＰ・フラーレン複合体は、その生理活性等の特性の発現とともに、安定性、安全性に優れたものとなる。 According to the invention of this application as described above, a pharmaceutical product can be used under halogen-free conditions without using a halogenated aliphatic hydrocarbon solvent, which is feared to have an impact on the human body due to residues and an increase in the environmental load of disposal. Production of a PVP / fullerene complex and an aqueous solution thereof using ethanol as an acceptable solvent is possible. The produced PVP / fullerene complex exhibits excellent stability and safety as well as expression of its physiological activity and the like.
この出願の発明は上記のとおりの特徴をもつものであるが、以下、その実施の形態について説明する。 The invention of this application has the features as described above, and an embodiment thereof will be described below.
この出願の第１の発明においては、ＰＶＰ・フラーレン複合体水溶液の製造方法が提供されるが、この方法においては、まず、フラーレンまたはフラーレン混合物の芳香族炭化水素溶媒溶液が準備される。ここで、原料物質としてのフラーレンまたはフラーレン混合物には、これまでにも知られているＣ６０、Ｃ７０、さらにはより高次の炭素球殻構造をもつものや、カーボンナノチューブ、フラーレンチューブ等のチューブ構造をもつものの各種のフラーレンやそれらの２種以上のものの混合物が含まれる。そして、これらのフラーレンは、この出願の発明方法の目的、効果を阻害しないものであれば、水酸化フラーレンのような水酸基を有するもの、そのエーテルあるいはアシル化フラーレン、その金属塩をはじめ、アミノ基、炭化水素基、置換炭化水素基等の各種の置換基によって修飾されたフラーレンであってもよい。このようなフラーレンあるいはフラーレン混合物の溶媒としての芳香族炭化水素としては、各種のものであってよいが、トルエン、キシレン、ベンゼン、クロロベンゼンあるいはそれらの２種以上の混合物が好適なものとして例示される。なかでもトルエンが溶媒として良好である。 In the first invention of this application, a method for producing a PVP / fullerene complex aqueous solution is provided. In this method, first, an aromatic hydrocarbon solvent solution of fullerene or a fullerene mixture is prepared. Here, the fullerene or fullerene mixture as the raw material includes C60, C70, and those having a higher-order carbon spherical shell structure, tube structures such as carbon nanotubes and fullerene tubes. And various fullerenes and mixtures of two or more thereof. These fullerenes are those having a hydroxyl group, such as a hydroxylated fullerene, ethers or acylated fullerenes, metal salts thereof, amino groups, etc. Further, it may be a fullerene modified with various substituents such as a hydrocarbon group and a substituted hydrocarbon group. The aromatic hydrocarbon as a solvent of such fullerene or fullerene mixture may be various, but toluene, xylene, benzene, chlorobenzene, or a mixture of two or more thereof is exemplified as a preferable one. . Of these, toluene is a good solvent.
この出願の発明のＰＶＰ・フラーレン複合体そしてその水溶液の製造においては、フラーレンまたはフラーレン混合物（Ｆ）と芳香族炭化水素溶媒（Ａ）との割合は、一般的には重量比（Ｆ／Ａ）として、０.０００５〜０.００３２ (max,; 最大溶解度)の範囲とすることが考慮される。より好適には、その範囲は、０.０００７５〜０.０００９５である。０.００３２を超えるフラーレンまたはフラーレン混合物が過剰な場合には、均一溶液の生成が難しく、ＰＶＰエタノール溶液との混合による均一溶液の生成が困難になる。一方、０.０００５未満の過少な場合には経済的ではない。 In the production of the PVP / fullerene complex of the present invention and the aqueous solution thereof, the ratio of fullerene or fullerene mixture (F) to aromatic hydrocarbon solvent (A) is generally a weight ratio (F / A). Is considered to be in the range of 0.0005 to 0.0032 (max ,; maximum solubility). More preferably, the range is from 0.000007 to 0.000009. If the amount of fullerene or fullerene mixture exceeding 0.0036 is excessive, it is difficult to form a uniform solution, and it is difficult to form a uniform solution by mixing with a PVP ethanol solution. On the other hand, if it is less than 0.0005, it is not economical.
フラーレンあるいはフラーレン混合物の芳香族炭化水素溶媒溶液は、この出願の発明においてはポリビニルピロリドン（ＰＶＰ）のエタノール溶液と混合される。このＰＶＰは、トルエン、キシレン、ベンゼン、クロロベンゼン等の芳香族炭化水素溶媒にはほとんど溶解しない。そこでこれまではクロロホルム、ジクロロメタン、1,2-ジクロロエタン等のハロゲン脂肪族化炭化水素溶媒に溶解させていたが、この出願の発明では、このようなクロロホルム、ジクロロメタン、1,2-ジクロロエタン等のハロゲン脂肪族化炭化水素溶媒(-CHX2基を含む溶剤）は一切使用することはない。これに代わるものとして、医薬品許容溶媒として安全性に優れたエタノールを使用する。 In the invention of this application, the aromatic hydrocarbon solvent solution of fullerene or fullerene mixture is mixed with an ethanol solution of polyvinylpyrrolidone (PVP). This PVP hardly dissolves in an aromatic hydrocarbon solvent such as toluene, xylene, benzene or chlorobenzene. So far, it was dissolved in a halogenated hydrocarbon solvent such as chloroform, dichloromethane, 1,2-dichloroethane, etc., but in the invention of this application, such halogens as chloroform, dichloromethane, 1,2-dichloroethane, etc. Aliphatic hydrocarbon solvents (solvents containing -CHX 2 groups) are never used. As an alternative, ethanol with excellent safety is used as a pharmaceutical acceptable solvent.
ＰＶＰ（ポリビニルピロリドン）は、次式 PVP (polyvinylpyrrolidone) has the following formula:
フラーレンまたはフラーレン混合物の芳香族炭化水素溶液（Ｆ・Ａ）とＰＶＰエタノール溶液（ＰＶＰ・Ｅ）との混合は、通常、その割合が重量比（Ｆ・Ａ／ＰＶＰ・Ｅ）として１.０〜３.０の範囲が考慮される。さらには、１.５〜２.０の範囲が好適である。この重量比が１.０未満の場合には反応効率の減少の理由によって好ましくなく、一方、３.０を超える場合には溶媒留去の非効率性の理由によって好ましくない。 Mixing of fullerene or fullerene mixture of aromatic hydrocarbon solution (F · A) and PVP ethanol solution (PVP · E) is usually 1.0 to 1.0 as a weight ratio (F · A / PVP · E). A range of 3.0 is considered. Furthermore, the range of 1.5-2.0 is suitable. When this weight ratio is less than 1.0, it is not preferable because of a decrease in reaction efficiency, whereas when it exceeds 3.0, it is not preferable because of inefficiency of solvent evaporation.
両者の混合は、通常、１５℃〜２５℃の温度範囲において攪拌して行うことが望ましい。この際の攪拌は、たとえば羽根型プロペラによる回転速度約４００rpmの条件では、１２〜１５時間程度行うことが考慮される。 The mixing of both is usually preferably performed with stirring in a temperature range of 15 ° C to 25 ° C. It is considered that the stirring at this time is performed for about 12 to 15 hours under the condition of, for example, a rotational speed of about 400 rpm with a blade type propeller.
以上のような両者の混合によって均一な混合溶液が生成されることになる。 A uniform mixed solution is produced by mixing the two as described above.
次いで、この出願の発明においては、混合溶液への水の添加と溶媒の除去の工程を実行することでＰＶＰ・フラーレン複合体の水溶液とするが、これらの工程には様々な手段と手順が採用されてよい。 Next, in the invention of this application, the steps of adding water to the mixed solution and removing the solvent are performed to obtain an aqueous solution of the PVP / fullerene complex, and various means and procedures are adopted in these steps. May be.
たとえば混合溶液を蒸発処理して乾固させ、水を添加して懸濁液を調製し、その後蒸発処理して共沸によりトルエン等の溶媒を留去して乾固させ、これに再度水を添加して水溶液とするとの工程が実施される。あるいは、上記混合溶液に水を添加し、その後蒸発処理して共沸させ、再度水を添加するようにしてもよい。 For example, the mixed solution is evaporated to dryness, water is added to prepare a suspension, and then evaporated to remove the solvent such as toluene by azeotropic distillation to dryness. A step of adding an aqueous solution is performed. Alternatively, water may be added to the mixed solution, followed by evaporation to azeotrope, and water may be added again.
いずれの工程においても水の添加量は、最終的なＰＶＰ・フラーレン複合体水溶液におけるＰＶＰ・フラーレン複合体の濃度が５〜２０重量％の範囲になるように調整することが考慮される。より好ましい水溶液濃度は６.５〜１４.５重量％の範囲である。 In any step, it is considered that the amount of water added is adjusted so that the concentration of the PVP / fullerene complex in the final PVP / fullerene complex aqueous solution is in the range of 5 to 20% by weight. A more preferable aqueous solution concentration is in the range of 6.5 to 14.5% by weight.
水溶液濃度が５重量％未満では蒸発乾固の非効率性の理由から好ましくなく、一方、２０重量％を超える場合には高い水溶液粘度のため濾過の際に加熱し溶解度を増加させなければならない必要性の理由によって好ましくない。 If the concentration of the aqueous solution is less than 5% by weight, it is not preferable due to the inefficiency of evaporation to dryness. On the other hand, if it exceeds 20% by weight, the aqueous solution viscosity must be increased during heating to increase the solubility. Unfavorable for reasons of sex.
もちろん、このような範囲の濃度は、水溶液の用途に応じての、最終的な水分添加によって調整されてもよい。 Of course, the concentration in such a range may be adjusted by the final water addition depending on the application of the aqueous solution.
また、添加する水の温度は２０℃〜３５℃程度の範囲とすることが望ましい。 Further, the temperature of the water to be added is desirably in the range of about 20 ° C to 35 ° C.
たとえば以上の方法によって製造されたこの出願の発明のＰＶＰ・フラーレン複合体の水溶液は、これを蒸発乾固することで固体状のＰＶＰ・フラーレン複合体とすることができ、さらには、このものを水に溶解して水溶液とし、様々な用途に使用することができる。 For example, the aqueous solution of the PVP / fullerene complex of the invention of the present application produced by the above method can be evaporated to dryness to obtain a solid PVP / fullerene complex. It can be dissolved in water to form an aqueous solution and used for various purposes.
そこで以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって発明が限定されることはない。 Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
＜Ａ＞Ｃ６０フラーレンとＣ７０フラーレンとを含むＭＩＸ（混合）フラーレン（平均分子量７４４：粉体）の１６．０ｍｇをトルエン（２０ｍｌ）の溶液と、重量平均分子量６０，０００のＰＶＰ２．０ｇのエタノール（１０ｍｌ）溶液とを各々調製し、両者を室温で混合して１２時間攪拌した。これによって均一な混合溶液を得た。 <A> 16.0 mg of MIX (mixed) fullerene (average molecular weight 744: powder) containing C60 fullerene and C70 fullerene, a solution of toluene (20 ml), and 2.0 g of ethanol (weight average molecular weight 60,000 PVP) 10 ml) solutions were prepared, and both were mixed at room temperature and stirred for 12 hours. Thereby, a uniform mixed solution was obtained.
次いで、この均一混合溶液を蒸発処理して乾固させた後に３０ｍｌの水を添加し、懸濁液とした。 Next, the homogeneous mixed solution was evaporated to dryness, and 30 ml of water was added to form a suspension.
この懸濁液を蒸発処理し、共沸によりトルエンを留去し、乾固させた。その後３０ｍｌの水を加え、１５分間のソニケーションを行った。これによってＰＶＰ・フラーレン複合体水溶液を得た。濾過（０．８０マイクロメートルフィルター）して、最終的なＰＶＰ・フラーレン複合体水溶液とした。 This suspension was evaporated and toluene was distilled off azeotropically to dryness. Then 30 ml of water was added and sonication was performed for 15 minutes. As a result, an aqueous PVP / fullerene complex solution was obtained. Filtration (0.80 micrometer filter) was performed to obtain a final PVP / fullerene complex aqueous solution.
得られた水溶液は透明度が高く、クロロホルムを溶媒とした場合において一昼夜室温下に放置すると生じる微量の黒色沈殿の生成は全く観察されなかった。 The obtained aqueous solution had high transparency, and when a chloroform was used as a solvent, a trace amount of black precipitate formed when left at room temperature overnight was not observed at all.
そしてまた、上記の水溶液を蒸発乾固処理し、粉砕、減圧乾燥（１２時間）してＰＶＰ・フラーレン複合体粉末を得た．
＜Ｂ＞得られたＰＶＰ・フラーレン複合体水溶液（Ｓ１）についてその活性酸素消去効果をＥＳＲ（スピントラッピング法）によって測定した。クロロホルム溶媒を用いて調製した水溶液（Ｓ２）との比較を図１に例示した。図１のように、同等以上の活性酸素消去効果が得られることが確認された。
The aqueous solution was evaporated to dryness, pulverized and dried under reduced pressure (12 hours) to obtain a PVP / fullerene complex powder.
<B> The active oxygen scavenging effect of the obtained PVP / fullerene complex aqueous solution (S1) was measured by ESR (spin trapping method). A comparison with an aqueous solution (S2) prepared using a chloroform solvent is illustrated in FIG. As shown in FIG. 1, it was confirmed that an active oxygen scavenging effect equivalent to or higher than that was obtained.
スピントラッピング剤を用いたESR分析法（スピントラッピング法）は、非常に反応性の高い不安定なフリーラジカルをスピントラップ剤と反応させ、生成する安定なスピン付加体のESRスペクトルを室温で測定するもので、フリーラジカルを検出するには有力な方法である。
この方法では、過酸化水素と硫酸第一鉄の反応（Fenton反応）により生成するヒドロキシルラジカルを、5,5-ジメチル-1-ピロリン-N-オキシド(DMPO)をスピントラップ剤として用い、DMPOとヒドロキシルラジカルが反応して生成するDMPO-OHのシグナルを観測する(Control)。
図１の縦軸はDMPO-OHと内部標準(MnO)との相対値、横軸はＰＶＰ・フラーレン複合体投与濃度を示している。Controlは生じたDMPO-OHの最大値(26.5)で、下限値(12.5)はジメチルスルホキシド(DMSO)によりヒドロキシルラジカル（活性酸素）を完全に補足（消去）した場合の値である。図１のように、ＰＶＰ・フラーレン複合体水溶液（Ｓ１）、クロロホルム溶媒を用いて調製した水溶液（Ｓ２）については、いずれの濃度でもヒドロキシルラジカル（活性酸素）の消去効果が同等に得られることが確認された。とくに12.5-25μMの濃度で、顕著な活性酸素消去効果が観測された。
The ESR analysis method using a spin trapping agent (spin trapping method) reacts a highly reactive unstable free radical with a spin trap agent, and measures the ESR spectrum of the resulting stable spin adduct at room temperature. Therefore, it is an effective method for detecting free radicals.
In this method, the hydroxyl radical generated by the reaction of hydrogen peroxide and ferrous sulfate (Fenton reaction) is used as a spin trap agent using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap agent. Observe the signal of DMPO-OH produced by reaction of hydroxyl radical (Control).
The vertical axis in FIG. 1 represents the relative value between DMPO-OH and the internal standard (MnO), and the horizontal axis represents the concentration of PVP / fullerene complex administered. Control is the maximum value (26.5) of the generated DMPO-OH, and the lower limit value (12.5) is the value when hydroxyl radical (active oxygen) is completely captured (erased) by dimethyl sulfoxide (DMSO). As shown in FIG. 1, the PVP / fullerene complex aqueous solution (S1) and the aqueous solution (S2) prepared using a chloroform solvent can obtain the same effect of eliminating hydroxyl radicals (active oxygen) at any concentration. confirmed. In particular, a significant active oxygen scavenging effect was observed at a concentration of 12.5-25 μM.
Claims (7)
A method for producing a PVP / fullerene complex aqueous solution, wherein the PVP / fullerene complex produced by the method according to claim 6 is mixed with water.
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