JP2005113090A - A complex of fine particles encapsulating carbon compounds - Google Patents
A complex of fine particles encapsulating carbon compounds Download PDFInfo
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- JP2005113090A JP2005113090A JP2003352666A JP2003352666A JP2005113090A JP 2005113090 A JP2005113090 A JP 2005113090A JP 2003352666 A JP2003352666 A JP 2003352666A JP 2003352666 A JP2003352666 A JP 2003352666A JP 2005113090 A JP2005113090 A JP 2005113090A
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- 239000010419 fine particle Substances 0.000 title claims abstract description 9
- 150000001722 carbon compounds Chemical class 0.000 title description 2
- 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 claims abstract description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 11
- -1 polyethylene Polymers 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 229910003472 fullerene Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000011859 microparticle Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- AHLWZBVXSWOPPL-RGYGYFBISA-N 20-deoxy-20-oxophorbol 12-myristate 13-acetate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(C=O)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C AHLWZBVXSWOPPL-RGYGYFBISA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241001602688 Pama Species 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
【課題】 フラーレンC60の可溶化複合体の提供
【解決手段】 ポリエチレングリコールーblock−ポリ（メタクリル酸アルキルアミノエチル）のブロックコポリマーの微小粒子中にフラーレンC60が内包された複合体。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a solubilized complex of fullerene C 60. A complex in which fullerene C 60 is encapsulated in fine particles of a block copolymer of polyethylene glycol-block-poly (alkylaminoethyl methacrylate).
[Selection figure] None
Description
本発明は、C60を内包し、そしてブロックコポリマーをベースとする微小粒子の複合体に関する。 The present invention containing a C 60, and to a complex of fine particles based on block copolymers.
フラーレンC60は、それらの新奇な構造のため、多岐にわたる技術分野、例えば、医薬、体内診断、化粧品、等での使用が期待されている。 Due to their novel structure, fullerene C 60 is expected to be used in various technical fields such as medicine, in-vivo diagnosis, cosmetics and the like.
しかし、特に、これらの技術分野で使用するには、フラーレンが水に不溶性であるため一定の制限があった。したがって、フラーレンを可溶化するためにフラーレンの炭素原子にヒドロキシル基を導入した各種フラロールの提供（特許文献１参照。）や、例えば、金属内包フラーレンまたはその塩の表面をスルホン基、ケトン基、アミノ基およびアルキル基からなる群より選ばれる官能基を有する多糖類で被覆したものも提供されている（特許文献２参照。）。
本発明の目的は、フラーレンの可溶化が達成された新たな組成物または複合体を提供することにある。 An object of the present invention is to provide a new composition or complex in which solubilization of fullerene is achieved.
本発明者らの一部は、ＤＮＡ等の生体内標的への有力な送達手段として、ＤＮＡとポリエチレングリコール−ｂｌｏｃｋ−ポリ（２−（Ｎ,Ｎ−ジメチルアミノ）エチルメタクリレートのポリマーミセル複合体を提供した（K. Kataoka et al., Macromolecules １９９９，３２，６８９２−６８９４参照）。しかし、意外にも、本発明者らは、かかるブロックコポリマーは、水不溶性であり、しかも炭素原子から本質的になるフラーレンC60とも複合体を形成し、それらを可溶化しうることを、ここに見出した。 Some of the inventors have used a polymer micelle complex of DNA and polyethylene glycol-block-poly (2- (N, N-dimethylamino) ethyl methacrylate as an effective delivery means to in vivo targets such as DNA. (See K. Kataoka et al., Macromolecules 1999, 32, 6892-6894). It has now been found that fullerene C 60 can also be complexed and solubilized.
したがって、本発明によれば、フラーレンC60を内包したポリマーをベースとする微小粒子の複合体であって、微小粒子が、一般式（１）： Therefore, according to the present invention, a composite of fine particles based on a polymer containing fullerene C 60 , wherein the fine particles are represented by the general formula (1):
（式中、非結合末端が反応性官能基により置換されているかまたは未置換のC１−１２アルキル基を表し、R1 および R2は、相互に独立してC１−６のアルきる基を表し、mは １０〜２０，０００であり、そしてnは１〜１０，０００である。）で表されるブロックコポリマーから形成され、ポリエチレングリコールのポリマー鎖セグメントをコア部とし、ポリ（メタクリル酸アルキルアミノエチル）のポリマー鎖セグメントをシェル部とする、ことを特徴とする複合体が提供される。 (Wherein the non-bonded end represents a substituted or unsubstituted C 1-12 alkyl group, R 1 and R 2 are each independently a C 1-6 alkyl group. Where m is 10 to 20,000 and n is 1 to 10,000. And a polymer chain segment of polyethylene glycol as a core portion and a polymer chain segment of poly (alkylaminoethyl methacrylate) as a shell portion is provided. The
微小粒子が三級アミノ基または二級アミノ基を担持した反復単位を含有するポリマー鎖セグメントをコアとし、そして非イオン性の親水性ポリマー鎖セグメントをシエルとする構造物を形成できるブロックコポリマーに由来することを特徴とする微小粒子の複合体が提供される。 Derived from a block copolymer that can form a structure in which a microparticle has a polymer chain segment containing a repeating unit carrying a tertiary amino group or a secondary amino group as a core, and a nonionic hydrophilic polymer chain segment as a shell A composite of microparticles is provided.
本発明に従う、フラーレンを内包する微小粒子の複合体は、調製後に凍結乾燥した場合であっても、極めて容易に水中に分散もしくは溶解して透明で、かつ安定な溶液を形成しうる。 The complex of fine particles encapsulating fullerene according to the present invention can be dispersed or dissolved in water very easily to form a transparent and stable solution even when freeze-dried after preparation.
以下、本発明をより具体的に記述する。 Hereinafter, the present invention will be described more specifically.
本発明にいう、「フラーレンC60」とは、当該技術分野で周知の６０の炭素原子からなる閉殻(またはかご形)構造を有する化合物である。また、本発明では、フラーレンC60の他に、フラーレンC50、C70および／またはC76等が１０％程度まで含まれていても本発明の範囲に包含されるものと理解されねばならない。 The “fullerene C 60 ” referred to in the present invention is a compound having a closed shell (or cage shape) composed of 60 carbon atoms well known in the art. In the present invention, in addition to the fullerene C 60, should be understood as being within the scope of the invention to fullerene C 50, C 70 and / or C 76 or the like is included up to about 10%.
このような、フラーレンC60を上記一般式(１)で表されるブロックコポリマーで形成される微小粒子に封入するには、フラーレンC60とブロックコポリマーの両者を、それらを溶解しうる溶媒、例えば、塩化メチレン等に溶解した後、溶媒を留去し、次いで残留物を水に徐々に溶解していくか、または後述する実施例に記載する方法によればよい。 Such a fullerene C 60 in encapsulated in fine particles formed by the block copolymer represented by the above general formula (1) are both fullerene C 60 and the block copolymer, a solvent capable of dissolving them, e.g. After dissolving in methylene chloride or the like, the solvent is distilled off, and then the residue is gradually dissolved in water, or the method described in the examples described later may be used.
こうして形成される微小粒子の複合体は、通常、ブロックコポリマー対炭素化合物を、重量比で、１００００：１、好ましくは１００：１の割合で含む。かような微小粒子の複合体は、水中で安定かつ透明な分散液または溶液を形成しうる。 The microparticle composite thus formed usually comprises a block copolymer to carbon compound in a weight ratio of 10,000: 1, preferably 100: 1. Such a composite of microparticles can form a stable and transparent dispersion or solution in water.
以下、具体例を参照しながら本発明をさらに具体的に説明するが、本発明をこれらに限定することを意図するものでない。
＜ブロックコポリマーの製造例＞
Hereinafter, the present invention will be described more specifically with reference to specific examples, but the present invention is not intended to be limited thereto.
<Example of production of block copolymer>
アルゴン下２００ｍＬナスフラスコに溶媒として蒸留テトラヒドロフラン（ＴＨＦ）５０ｍＬを入れ、開始剤として３,３′−ジエトキシ−１−プロパノール（Ｍｗ＝１４８、ｄ＝０.９４１）を１５７μＬ入れた。その後、カリウムナフタレン（Ｋ−Ｎａｐｈ（ｃ＝０.３６５６ｍｏｌ／Ｌ））を２.７３ｍＬ入れメタル化した。次にエチレンオキシド（ＥＯ（Ｍｗ＝４４、ｄ＝０.８８））５.６８ｍＬを入れた後水冷下で２日間撹拌した。２日後、少量をサンプリングし、ＧＰＣで解析を行った後、２−（Ｎ,Ｎ−ジメチルアミノ）エチルメタクリレート（ＰＡＭＡ；ＭＷ＝１５７.２１）を４.２９ｍＬ入れ、氷冷下で３０分撹拌し、ＧＰＣでサンプリングを行った。最後にメタノールで反応を停止させた。 In a 200 mL eggplant flask under argon, 50 mL of distilled tetrahydrofuran (THF) was added as a solvent, and 157 μL of 3,3′-diethoxy-1-propanol (Mw = 148, d = 0.941) was added as an initiator. Thereafter, 2.73 mL of potassium naphthalene (K-Naph (c = 0.365 mol / L)) was added and metallized. Next, 5.68 mL of ethylene oxide (EO (Mw = 44, d = 0.88)) was added, followed by stirring for 2 days under water cooling. Two days later, a small amount was sampled and analyzed by GPC. Then, 4.29 mL of 2- (N, N-dimethylamino) ethyl methacrylate (PAMA; MW = 157.21) was added and stirred for 30 minutes under ice cooling. Then, sampling was performed by GPC. Finally, the reaction was stopped with methanol.
反応停止後、イソプロピルアルコール再沈、遠心分離を行い、ベンゼン凍結乾燥をし、回収した。 After stopping the reaction, isopropyl alcohol was reprecipitated and centrifuged, and benzene was lyophilized and collected.
精製したポリマーの分子量はＰＥＧ／ＰＡＭＡ＝４,５００／５,５００であった。 The molecular weight of the purified polymer was PEG / PAMA = 4,500 / 5,500.
透析法による水中でのフラーレンの分散安定化
フラーレン：アセタール−ＰＥＧ−ＰＭＡＭＡブロックコポリマーの混合比（Ｆ：Ｐ）が１：０、１：０.５、１：１となるように溶媒ジメチルホルムアミド（ＤＭＦ）２５ｍＬ中にフラーレン１ｍｇ、ブロックコポリマー１３.８ｍｇを加え（Ｆ：Ｐ＝１：１の場合）、６時間超音波処理を行った後、一晩静置した。その後、蒸留水で一晩膨潤させた分画分子量１２０００−１４０００の透析膜中に溶液を入れ、透析を行った（水交換３回）。こうして得られた３０ｍＬのフラーレン内包微小粒子の溶液の溶媒を凍結乾燥により除去し、その後蒸留水５ｍＬ加え、再分散させた。その後、再度ＤＬＳ測定を行った。
Dispersion stabilization of fullerene in water by dialysis method Dimethylformamide (solvent) so that the mixing ratio (F: P) of fullerene: acetal-PEG-PMMAMA block copolymer is 1: 0, 1: 0.5, 1: 1. In 25 mL of DMF), 1 mg of fullerene and 13.8 mg of block copolymer were added (in the case of F: P = 1: 1), subjected to ultrasonic treatment for 6 hours, and then allowed to stand overnight. Then, the solution was put into a dialysis membrane having a molecular weight cut off of 12000-14000 which was swollen overnight with distilled water, and dialyzed (3 times of water exchange). The solvent of the 30 mL fullerene-containing microparticle solution thus obtained was removed by lyophilization, and then 5 mL of distilled water was added and redispersed. Thereafter, DLS measurement was performed again.
こうして濃縮後の溶液にはフラーレン特有の黒褐色を呈した。ブロックコポリマー非存在下では濃縮によって濁度を生ずるものの、本発明に従う複合体では凍結乾燥後にも極めて容易に水中に分散溶解した。混合比がＦ：Ｐ＝１：１、１：０.５のものを再度ＤＬＳ測定を行ってみたところ、濃縮再分散を行う前よりはフォトンカウントが増加したが、以前測定に十分なフォトンカウントは得ることができなかった。このようにこの条件で調製したフラーレン粒子は光散乱で検出できる粒径（およそ３ｎｍ）以下のほぼ分子状分散に近い形で分散している。 Thus, the concentrated solution exhibited a blackish brown color characteristic of fullerene. In the absence of the block copolymer, turbidity is produced by concentration, but the complex according to the present invention was very easily dispersed and dissolved in water even after lyophilization. When DLS measurement was performed again for a mixture ratio of F: P = 1: 1, 1: 0.5, the photon count increased compared to before the concentration redispersion, but the photon count sufficient for the previous measurement. Could not get. Thus, the fullerene particles prepared under these conditions are dispersed in a form close to a molecular dispersion having a particle size (approximately 3 nm) or less that can be detected by light scattering.
バブリング蒸発法による水中でのフラーレンの分散安定化
フラーレン１ｍｇを塩化メチレン溶媒２５ｍＬに混ぜ、超音波をかけることで塩化メチレン中に溶解させた。その後、アセタール−ＰＥＧ−ＰＭＡＭＡブロックコポリマー１３９ｍｇを溶媒に入れ、超音波を２時間かけた後、一晩静置した。
Fullerene dispersion stabilization in water by bubbling evaporation method 1 mg of fullerene was mixed with 25 mL of methylene chloride solvent and dissolved in methylene chloride by applying ultrasonic waves. Thereafter, 139 mg of an acetal-PEG-PMAMA block copolymer was put in a solvent, subjected to ultrasonic waves for 2 hours, and then allowed to stand overnight.
このようにして調製した塩化メチレン溶液をアルゴンバブリングをしている蒸留水４０ｍＬに滴下していった。こうして調製した溶液は、実施例１に記載のものと同様に、淡黄色の透明溶液を与える微小粒子の複合体を提供した。得られた水中分散安定化フラーレン複合体の溶液のＤＬＳ測定を行った結果、粒径１７０ｎｍ程度のナノ粒子が形成されていることが確認できた。 The methylene chloride solution thus prepared was added dropwise to 40 mL of distilled water with argon bubbling. The solution thus prepared provided a microparticle complex that gave a pale yellow transparent solution, similar to that described in Example 1. As a result of DLS measurement of the solution of the obtained dispersion-supported fullerene complex in water, it was confirmed that nanoparticles having a particle size of about 170 nm were formed.
本発明に従う、フラーレン内包微小粒子複合体は、フラーレンを水可溶化しうるので、医薬、診断薬等の分野でのフラーレンの使用範囲を拡大できる。
Since the fullerene-encapsulated microparticle complex according to the present invention can solubilize fullerene in water, the range of use of fullerene in the fields of pharmaceuticals, diagnostics and the like can be expanded.
Claims (1)
フラーレンC60を内包したポリマーをベースとする微小粒子の複合体であって、微小粒子が、一般式（１）：
General formula (1)
A composite of fine particles based on a polymer containing fullerene C 60 , wherein the fine particles have the general formula (1):
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003352666A JP4746834B2 (en) | 2003-10-10 | 2003-10-10 | A complex of fine particles encapsulating carbon compounds |
| US10/575,549 US7410699B2 (en) | 2003-10-10 | 2004-09-06 | Finely particulate composite containing carbon compound encapsulated in a polymer micelle of a block copolymer |
| EP04772937A EP1672025B1 (en) | 2003-10-10 | 2004-09-06 | Finely particulate composite containing carbon compound encapsulated therein |
| CN200480029482A CN100577728C (en) | 2003-10-10 | 2004-09-06 | Composite of tiny particles enclosing carbon compounds |
| CA2542049A CA2542049C (en) | 2003-10-10 | 2004-09-06 | Finely particulate composite containing carbon compound encapsulated therein |
| KR1020067006483A KR100977697B1 (en) | 2003-10-10 | 2004-09-06 | Finely particulate composite containing carbon compound encapsulated therein |
| PCT/JP2004/013255 WO2005035651A1 (en) | 2003-10-10 | 2004-09-06 | Finely particulate composite containing carbon compound encapsulated therein |
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| JP2003352666A JP4746834B2 (en) | 2003-10-10 | 2003-10-10 | A complex of fine particles encapsulating carbon compounds |
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| JP4746834B2 JP4746834B2 (en) | 2011-08-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005225772A (en) * | 2004-02-10 | 2005-08-25 | Japan Science & Technology Agency | Composite of microparticles encapsulating carbon compounds |
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| CN101695996B (en) * | 2009-11-09 | 2012-05-30 | 上海交通大学 | Preparation method of carbon nanotube composite material based on amino polyphosphazene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09235235A (en) * | 1996-02-29 | 1997-09-09 | Res Inst For Prod Dev | Fullerene-binding water-soluble polymer photosensitizer for photodynamic therapy |
| JP2002241307A (en) * | 2001-02-19 | 2002-08-28 | Yasuhiko Tabata | Active oxygen generator for ultrasonic therapy containing photosensitizer |
| JP2003147418A (en) * | 2001-11-09 | 2003-05-21 | Japan Science & Technology Corp | Preparation of metal nanoparticles using shell- crosslinked micelle as template |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09235235A (en) * | 1996-02-29 | 1997-09-09 | Res Inst For Prod Dev | Fullerene-binding water-soluble polymer photosensitizer for photodynamic therapy |
| JP2002241307A (en) * | 2001-02-19 | 2002-08-28 | Yasuhiko Tabata | Active oxygen generator for ultrasonic therapy containing photosensitizer |
| JP2003147418A (en) * | 2001-11-09 | 2003-05-21 | Japan Science & Technology Corp | Preparation of metal nanoparticles using shell- crosslinked micelle as template |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005225772A (en) * | 2004-02-10 | 2005-08-25 | Japan Science & Technology Agency | Composite of microparticles encapsulating carbon compounds |
| JP4644430B2 (en) * | 2004-02-10 | 2011-03-02 | 独立行政法人科学技術振興機構 | Composite of microparticles encapsulating carbon compounds |
Also Published As
| Publication number | Publication date |
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| JP4746834B2 (en) | 2011-08-10 |
| CN1863866A (en) | 2006-11-15 |
| CN100577728C (en) | 2010-01-06 |
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