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WO2004074171A1 - Procede d'introduction d'une matiere fonctionnelle dans un nanotube organique - Google Patents

Procede d'introduction d'une matiere fonctionnelle dans un nanotube organique Download PDF

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Publication number
WO2004074171A1
WO2004074171A1 PCT/JP2004/001508 JP2004001508W WO2004074171A1 WO 2004074171 A1 WO2004074171 A1 WO 2004074171A1 JP 2004001508 W JP2004001508 W JP 2004001508W WO 2004074171 A1 WO2004074171 A1 WO 2004074171A1
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WO
WIPO (PCT)
Prior art keywords
solvent
organic
nanotube
stage
organic nanotube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2004/001508
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English (en)
Japanese (ja)
Inventor
Bo Yang
Toshimi Shimizu
Shoko Kamiya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Science and Technology Agency
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Japan Science and Technology Agency
National Institute of Advanced Industrial Science and Technology AIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Science and Technology Agency, National Institute of Advanced Industrial Science and Technology AIST filed Critical Japan Science and Technology Agency
Priority to US10/544,800 priority Critical patent/US20060140847A1/en
Publication of WO2004074171A1 publication Critical patent/WO2004074171A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials

Definitions

  • the present invention relates to a method for introducing a desired functional substance into a hollow cylinder-shaped space of an organic nanotube having an inner pore diameter of 5 nm or more in a solvent.
  • Conventional technology for introducing a desired functional substance into a hollow cylinder-shaped space of an organic nanotube having an inner pore diameter of 5 nm or more in a solvent.
  • Methods for introducing a metal or metal oxide into carbon nanotubes are roughly classified into a dry method and a wet method.
  • Typical drying methods are arc discharge (Guerret-Piecourt et al. Ature 372, 761 (1994)) and chemical vacuum deposition.
  • the organic nanotubes formed by self-assembly of organic molecules in water (or in a solvent) can be easily synthesized in large quantities, and many of them are derived from living organisms.
  • Japanese Patent Application 2002-80489, Japanese Patent Application 2002-322190, Japanese Patent Application 2002-35035, Japanese Patent Application 2002-49 238, Japanese Patent Application 2002-49239, Japanese Patent Application 2002-61797, 2003- 13266 Japanese Patent Application 2002-80489, Japanese Patent Application 2002-322190, Japanese Patent Application 2002-35035, Japanese Patent Application 2002-49 238, Japanese Patent Application 2002-49239, Japanese Patent Application 2002-61797, 2003- 13266
  • there is no suitable method for filling the organic nanotubes with a functional material though introducing various substances into the organic nanotubes would open many applications.
  • the organic nanotubes were synthesized in water (solvent), and the inside of the tube was filled with a solvent, and it was difficult to introduce the substance into the tube by diffusion of the target material in the solution.
  • the method of introducing carbon nanotubes is as follows: First, open the cap at the tip of the carbon nanotube at high temperature (140 ° C or higher) using a strong acid such as a mixed acid, and then place the target material at high temperature or high temperature. Since it had to be introduced in a vacuum, it was impossible to adapt to organic nanotubes. Therefore, there has been a demand for a method of introducing a functional substance into a tube under mild conditions suitable for an organic nanotube. Problems to be solved by the invention
  • the present invention provides a method for easily introducing a desired functional substance into an organic nanotube under mild conditions such as normal temperature and normal pressure. Means for solving the problem
  • the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems.
  • the water (or solvent) inside the organic nanotubes is once removed by freeze-drying, and then dispersed in a solution or dispersion of a desired functional substance.
  • a desired substance could be introduced into the tube, and the present invention was completed.
  • the present invention provides a step (first step) of forming an organic nanotube having an inner pore diameter of 5 nm or more by self-assembling a surface-active organic compound comprising a hydrophobic hydrocarbon group and a hydrophilic group in a liquid phase, Freeze-drying the formed organic nanotubes (second step); dissolving or dispersing the desired functional substance in a solvent (third step); Dispersing the freeze-dried organic nanotubes in this solution or dispersion at a temperature (fourth step).
  • FIG. 1 shows a TEM photograph of the tube obtained in Example 1.
  • A shows the shape before freeze-drying
  • (b) shows the shape after freeze-drying.
  • FIG. 2 shows a TEM photograph of the organic nanotubes filled with gold nanocrystals in Example 1. There are gold nanoparticles inside the tube.
  • A shows the low magnification TEM
  • b shows the high magnification TEM
  • c shows the electron diffraction pattern.
  • FIG. 3 shows a TEM photograph of the organic nanotubes filled with colloidal gold in Example 2.
  • the deposit on the upper right side of the tube is a colloidal gold aggregate.
  • the surface active organic compound is self-assembled by forming a hollow nanotube by dissolving the surface active organic compound in a solvent mainly composed of water.
  • This surface-active organic compound is composed of a hydrophobic hydrocarbon group and a hydrophilic group.
  • This hydrocarbon group is preferably a hydrocarbon chain having about 6 to 50 carbon atoms, preferably a straight chain, and may be saturated or unsaturated. When unsaturated, it preferably has three or less double bonds.
  • the hydrophilic group is preferably at least one selected from the group consisting of a sugar chain, a peptide chain, and a metal salt. These hydrophilic groups and hydrophobic groups are bonded directly or via an amide bond, an arylene group or an aryleneoxy group. Examples of the surface-active organic compound include the following compounds developed in the laboratory of the inventors.
  • O-glycoside-type glycolipid having a structure represented by the following formula (Japanese Patent Application No. 2002-80489, Japanese Patent Application No. 2002 -61797).
  • R'-NHCO- (CH 2) wherein, R, is divided by the reducing terminal hydroxyl group of Anoredopirano over scan! / ⁇ were residues, 11 represents. a. 6 to 20) n -COOH in An asymmetric double-headed lipid represented (JP-A-2002-322190).
  • G ′ represents a sugar residue excluding the hemiacetal hydroxyl group bonded to the anomeric carbon atom of the sugar
  • R ′ ′′ represents an unsaturated hydrocarbon group having 10 to 39 carbon atoms.
  • N-daricoside type glycolipid Japanese Patent Application No. 2003-13326.
  • Preferred conditions include the following conditions.
  • the aqueous solution of the surface-active organic compound is heated to a predetermined temperature (40 to 100 ° C), and the aqueous solution is cooled at a predetermined cooling rate (5.0 ° C or less) to a predetermined temperature (freezing temperature of the aqueous solution to 30 ° C). ), And store the aqueous solution at this storage temperature for a predetermined time (one day or more).
  • the surface-active organic compound self-assembles to form a hollow nanotube.
  • the inner pore diameter is usually 5 nm or more, preferably 500 nm or less, particularly 10 to 200 nm, and ⁇ is 10 OO nm or less, particularly 50 to 300 nm. Even if a material having an inner hole diameter of less than 5 nm is included, it can be used in the method of the present invention as long as it mainly has an inner hole diameter of 5 nm or more.
  • the solvent used here water such as distilled water, purified water, ultrapure water, other various salt solutions, and a pH buffer solution composed of phosphoric acid or the like can be used.
  • concentration of the surface active organic compound in the solvent is preferably 0.001 wZV% to 0.02 wZV%.
  • Stage 2 In this stage, the hollow nanotubes produced in the first stage are lyophilized.
  • the freeze-drying temperature is preferably 170 ° C. or less, and it is convenient to freeze in liquid nitrogen.
  • the degree of vacuum for freeze-drying is preferably 20 Pa or less, more preferably 1.0 Pa or less.
  • the freeze-drying time is preferably 24 hours or more, more preferably 72 hours or more.
  • This solvent is different from the solvent used in the first step and is water or an organic solvent, and the type of the solvent and the concentration of the functional substance may be appropriately selected depending on the functional substance and the purpose.
  • the functional substance is not particularly limited and can be appropriately selected depending on the purpose. If this functional substance dissolves in the solvent, it is converted into a solution, and the fine particles can be dispersed without dissolving in the solvent.
  • the size is preferably about 50 nm from the atomic size.
  • the functional substances and their uses are listed below.
  • the metal may be used as an aqueous solution in the form of a metal salt.
  • the metal salt include chloride, nitrate, sulfate, acetate, hydroxide and the like.
  • physiologically active substance examples include an immune protein, a nucleic acid, a low molecular organic compound, a non-immune protein, an immunoglobulin-binding protein, a sugar-binding protein, an enzyme, and a microorganism.
  • Examples include therapeutic agents, diagnostic agents, contrast agents, and drugs that are active ingredients in cosmetics used for medical treatment.
  • the organic nanotubes dried in the second stage are dispersed in the solution of the functional substance created in the third stage. Solutions or dispersions of this functional substance are subject to capillary action. It is considered that the tube is sucked into the tube by the suction force.
  • the amount of organic nanotubes to be added is not particularly limited, and may be appropriately selected depending on the purpose of final use, the concentration of the functional substance in the solution, the size of the organic nanotube, and the like.
  • the temperature of the solvent is equal to or lower than the gel-liquid crystal phase transition temperature of the surface active organic compound, but is preferably room temperature, that is, a temperature at which heating and cooling are not particularly performed.
  • the gel-liquid crystal phase transition temperature can be measured by differential scanning calorimetry. Specifically, a sample in which 1 to 5 mg of a surface-active organic compound is mixed with 30 to 50 microliters of water to completely hydrate the compound is applied to this thermal analyzer, and the gel-liquid crystal phase transition is determined as an endothermic peak. A phenomenon appears, and the position 0 temperature at which the maximum peak occurs is determined as the phase transition temperature.
  • the gel-liquid crystal phase transition temperature means the melting point of a surfactant in water, which is referred to in colloid chemistry. When an aqueous dispersion is heated above this temperature, the tube structure becomes spherical vesicles (vesicles). It is not desirable because it causes a morphological change instantaneously, destroying the tube structure.
  • the gel-liquid crystal phase transition temperature depends on the type of the surface active organic compound and is usually about 30 to 90 ° C.
  • the pressure is preferably set at atmospheric pressure, but a pressure of 0.2 MPa or less may be applied.
  • a solution prepared by dissolving 11-cis-octadecenoic acid buciside (WAKO, 282 mg, 1.0 mmol) in 1 mL of dimethyl sulfoxide was used as a reaction system.
  • HOB t (WAKO, 153 mg, 1.0 mmol) and BOP (WAKO, 1.33 g, 3.0 mmol) dissolved in 1.5 mL of dimethyl sulfoxide were added to the reaction system.
  • the mixture was magnetically stirred at 25 ° C for 10 minutes.
  • 3-D-darcoviranosylamine obtained in Production Example 1 (1, 24 g, 6.9 mmol) was added to the reaction system, and the mixture was reacted under magnetic stirring at 25 ° C for 5 hours or more.
  • the crude product obtained was subjected to silica gel column chromatography using a mixed solvent of chloroform / methanol (volume ratio: 4/1) as an eluent, and then a gel filtration agent, Toyopearl HW-40S column chromatography, using methanol as an eluent.
  • the mixture was subjected to chromatography (manufactured by Tosoh Corporation) to obtain N- (11-cis-octadecenoyl) - ⁇ -D-darcoviranosylamine (85 mg, yield: 19%) as a white solid.
  • the dispersion liquid of organic nanotubes obtained in Production Example 3 was placed in liquid nitrogen (at 196 ° C) for 10 minutes and completely frozen. Thereafter, the mixture was transferred to a freeze-dryer (manufactured by Tokyo Rika Kikai Co., Ltd.) and dried at 25 ° C. for 72 hours in a vacuum (lPa). Then, the tube was taken out and its structure was confirmed by TEM. The results are shown in Fig. 1 (b). The structure of the tube did not change before and after freeze-drying, indicating that the freeze-drying treatment maintained the tube structure without collapse.
  • gold colloid was made. 9 Add 8 mL of gold chloride solution (0.01) to a 200-mL flask and heat to boiling (100 ° C). While stirring, 2 mL of a 1% by weight aqueous solution was added. Continue]] [[Heat and let react for 15 minutes. After that, it was left until it returned to room temperature. The resulting colloidal gold solution exhibited a red / wine color. The average particle size of the gold particles was 20 nm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé permettant d'introduire facilement une matière fonctionnelle souhaitée dans un nanotube organique dans des conditions modérées telles qu'à températures normales et à pressions normales. Le procédé comprend une première étape au cours de laquelle un nanotube organique ayant un diamètre de porte interne supérieur ou égal à 5 nm est formé par auto-assemblage d'un composé organique à surface active composé d'un groupe hydrocarboné hydrophobe et d'un groupe hydrophile dans un solvant, une deuxième étape au cours de laquelle le nanotube organique ainsi formé est lyophilisé, une troisième étape au cours de laquelle une matière fonctionnelle désirée est dissoute ou dispersée dans un solvant, et une quatrième étape au cours de laquelle le nanotube organique lyophilisé est dispersé dans la solution ou dispersion liquide à une température qui n'est pas supérieure à la température de transition de la phase cristalline gel-liquide du composé organique à surface active. Le nanotube organique ainsi produit peut posséder diverses applications en fonction des propriétés des matières fonctionnelles introduites.
PCT/JP2004/001508 2003-02-18 2004-02-12 Procede d'introduction d'une matiere fonctionnelle dans un nanotube organique Ceased WO2004074171A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/544,800 US20060140847A1 (en) 2003-02-18 2004-02-12 Method for introducing functional material into organic nanotube

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003039404A JP2004261885A (ja) 2003-02-18 2003-02-18 有機ナノチューブへ機能性物質を導入する方法
JP2003-039404 2003-02-18

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US6723299B1 (en) 2001-05-17 2004-04-20 Zyvex Corporation System and method for manipulating nanotubes
US20040034177A1 (en) 2002-05-02 2004-02-19 Jian Chen Polymer and method for using the polymer for solubilizing nanotubes
US6905667B1 (en) 2002-05-02 2005-06-14 Zyvex Corporation Polymer and method for using the polymer for noncovalently functionalizing nanotubes
GB2421506B (en) 2003-05-22 2008-07-09 Zyvex Corp Nanocomposites and methods thereto
US7296576B2 (en) 2004-08-18 2007-11-20 Zyvex Performance Materials, Llc Polymers for enhanced solubility of nanomaterials, compositions and methods therefor
WO2006038326A1 (fr) * 2004-10-01 2006-04-13 Toto Ltd. Procédé de contrôle de libération de substance active et matériau pour utilisation dans celui-ci
JP5062736B2 (ja) * 2006-06-14 2012-10-31 独立行政法人産業技術総合研究所 中空繊維状有機ナノチューブ及びその製造方法
JP2009136975A (ja) * 2007-12-07 2009-06-25 National Institute Of Advanced Industrial & Technology 低分子量化合物を内包する有機ナノチューブ
JP5487480B2 (ja) 2008-02-25 2014-05-07 保土谷化学工業株式会社 界面活性有機化合物を乳化剤として用いた水系エマルションの調製方法
WO2010126637A1 (fr) * 2009-02-09 2010-11-04 The Board Of Trustees Of The University Of Illinois Stockage d'hydrogène à l'aide de nanostructures hydrocarbonées et d'une application d'ultrasons
FR2942350B1 (fr) * 2009-02-16 2011-07-15 Commissariat Energie Atomique Nanocomposites, leur procede d'elaboration et leur utilisation dans des dispositifs de protection contre des ondes electromagnetiques
US20110039951A1 (en) * 2009-03-20 2011-02-17 Hydro Electron Ventures Water clusters confined in nano-environments
SG10201803748VA (en) * 2013-05-08 2018-06-28 Clene Nanomedicine Inc Methods and treatment for certain demyelination and dysmyelination-based disorders and/or promoting remyelination

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JPH04103527A (ja) * 1990-08-21 1992-04-06 Dai Ichi Seiyaku Co Ltd リポソーム製剤の製造法

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US20060140847A1 (en) 2006-06-29

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