KR20100056191A - Method for preparing capped nanotube and the same thereof - Google Patents

Abstract

PURPOSE: A method for manufacturing a nanotube is provided, which enables filling of functional materials without chemical treatment. CONSTITUTION: A method for manufacturing a nanotube comprises: a first step of forming a nanotube(20) in a plurality of pores formed in the anodized aluminum template(10); a second step of laminating stopper material(30) on the anodized aluminum template and nanotube; and a third step of sealing the nanotube by hammering the stopper material using a microbead(40) made of metal. The stopper material has higher hardness than that of microbead.

Description

Method for preparing a stopper-shaped nanotubes and nanotubes produced by the same {Method for preparing capped nanotube and the same

The present invention relates to a method for manufacturing a stopper-shaped nanotubes and nanotubes produced by the same, and more particularly to a stopper-shaped nanotubes comprising the step of sealing the nanotubes by hammering the stopper material (hammering) It relates to a method of preparation and a nanotube produced thereby.

Recently, interest in biomedical applications such as drug / gene transfer, cell isolation, and cancer diagnosis has increased for multifunctional nanotubes.

In particular, silicon nanotubes have been spotlighted as starting materials, bioseparation and drug delivery vehicles for the manufacture of multifunctional nanodevices because of the different deformations inside and outside the past several years.

In general, the tube structure obtained by template synthesis can be functionalized differently inside and outside, and can also provide a multifunctional platform through continuous surface modification. Drugs may be loaded into their internal spaces and the openings on one side may serve as gates to regulate drug / gene release. Therefore, by controlling the structure of these nanotube openings, precisely control the rate of absorption and release of the drug / gene to develop a transport system or to develop multifunctional nanotubes that contain the desired functional molecules or nanoparticles inside the nanotubes. The research for this is active.

Conventionally, a caulking method is used to seal an opening of a silica nanotube through a chemical reaction between an amine functional group and an aldehyde functional group of the silica nanotube by forming a plug in the opening as a gate for controlling drug / gene emission. Has been. However, the method has a low yield, there is a problem that a perfect seal is not made.

The present invention is to solve the conventional problems, the object of the present invention relates to a method capable of sealing the nanotubes with high reproducibility, and a nanotube with a stopper formed thereby.

One aspect of the present invention includes forming nanotubes in a plurality of pores formed in an anodized aluminum oxide (AAO) template; Stacking a stopper material on the anodized aluminum oxide (AAO) template and the nanotube; And sealing the nanotubes by hammering the plug material with microbeads formed of a metal, and a method of manufacturing a stopper-shaped nanotube, and the nanotubes thereby.

The method of manufacturing the stopper formed nanotubes of the present invention is easy to manufacture technology, excellent reproducibility and perfect sealing is possible. In addition, the method can be filled with a functional material without chemical treatment on the surface of the nanotubes, and furthermore the choice of plug material is very wide.

Hereinafter, the present invention will be described in detail.

1 shows a manufacturing method according to an embodiment of the present invention.

According to FIG. 1, a method according to an embodiment of the present invention includes forming a nanotube, stacking a stopper material, and sealing the nanotube by hammering the stopper material.

Hereinafter, the present invention will be described in detail for each step.

Forming nanotubes in a plurality of pores formed in an anodized aluminum oxide (AAO) template

Synthesis of nanostructures using anodized aluminum oxide (hereinafter abbreviated as "AAO") template, the synthesis of carbon nanotubes using chemical vapor deposition on AAO templates, the formation of sodium nanotubes on the inner walls of AAO templates, LiMn2O4 using AAO templates Nanowire synthesis and the like are known.

In general, the method of manufacturing a nanostructure using the AAO template has the advantage that the shape of the fabricated nanostructure is straight, uniform cylinder shape and high density.

The nanotube 20 is also manufactured using the AAO template 10 known in the present invention.

The nanotubes 20 may be synthesized from various kinds of materials. That is, it may be made of metal, polymer, semiconductor, carbon, and the like.

The nanotubes may be prepared using one material preferably selected from the group consisting of silica, carbon, titanium oxide, tungsten oxide and silicon.

 Silica nanotubes may be prepared by coating silica inside the AAO template 10 by a sol-gel method.

The silica sol solution may be prepared by stirring the silica precursor in alcohol and / or water to polymerize. Examples of the silica precursor include chlorsilane or tetraalkoxysilane, wherein the alkoxy group is preferably a C1 to C5 straight or branched alkoxy group. In addition, any silica adsorbent may be used as a silica precursor as long as it can be adsorbed on the AAO template to form silica (silicon dioxide) during drying and oxidation.

The nanotubes may be manufactured to have a diameter of 20 nm to 400 nm and a length of 100 nm to 30 micron, but is not limited thereto.

Depositing a stopper material on the anodized aluminum (AAO) template and the nanotube

The step is laminating the plug material 30 on the AAO template 10 and the nanotubes (20).

It is preferable that the plug material 30 has a Mohs hardness smaller than that of the microbeads 40. The plug material may be gold, silver, nickel, platinum, palladium or an alloy thereof.

The plug material 30 may be laminated on the template and the nanotube using thermal deposition, electron beam deposition, plasma deposition, sputtering, laser beam deposition, or the like.

The plug material 30 may be a biodegradable resin. The biodegradable stopper materials include aliphatic polyester resins (PBS, etc.), polycaprolactam, polylactic acid (PLA), P (HB-HV) (poly (3-hydroxybutyrate-co-3-hydoxyvalerate) copolymers), Chitosan, polylactic-co-glycolic acid (PLGA), gelatin, starch / PVA system and the like can be used.

The method of laminating the biodegradable stopper material may be formed by screen printing, printing, spin coating, dipping, or ink spraying, but is not limited thereto.

The thickness of the stacked plug material may be 10 nm to 500 nm, but is not necessarily limited thereto.

Figure 2a shows a scanning electron microscopy (SEM) of the nanotubes after laminating the plug material on the nanotubes. Referring to FIG. 2A, it can be seen that pores are opened even when the plug material is stacked on the template and the nanotube.

Sealing the nanotubes by hammering the plug material with microbeads formed of metal

The microbead may be formed of a metal having a greater Mohs hardness than the plug material, and alumina, silica, titanium oxide, tungsten oxide, and the like are preferable.

The size of the microbead may be 0.2 to 100 micron, but is not necessarily limited thereto.

There is no particular limitation on the shape of the microbeads, but it is preferably spherical or elliptical.

Sealing the nanotubes comprises inserting the anodized aluminum oxide template in which the plug material is stacked into the microtubes filled with the microbeads; And vibrating the microtube to hammer the plug material into the microbead.

The microtube is generally a material that can withstand the vibration given, but is not limited thereto. Generally, plastic products that are easy to manufacture and have good strength can be used. There is no particular limitation on the vibrating speed of the microtube, but it is preferable to vibrate for 10 minutes to 72 hours at a speed of 60 to 2000 rpm.

Temperature in the hammering step is not particularly limited, it is easy to implement about 5 ~ 80 ℃.

 The hammering time can be appropriately adjusted according to the hardness, size, and speed of the microbeads.

The expression hammering vibrates the microtube and strikes the plug material at high speed with the microbeads inside.

Figure 2b shows a scanning electron microscopy (SEM) of the nanotubes after hammering the plug material. Referring to FIG. 2B, it can be seen that the plug material is capped to the opening of the nanotube.

The method may further include filling a functional material inside the nanotubes after forming the nanotubes on the anodized aluminum oxide (AAO) template.

The method can fill the desired functional material without surface modification of the inner surface or attachment of chemical functional groups.

In the prior art in which there is no stopper or the cap is incompletely capped, a material to be filled therein may flow out through an opening, but there is a problem in that an inner derivative or a separate derivative capable of covalently bonding with a functional material has to be attached. According to the hammer, the plug material can seal the nanotubes, so that the desired functional material can be filled without surface modification or attachment of derivatives.

Functional materials that can be filled in the nanotubes include gold nanoparticles, silver nanoparticles, magnetic nanoparticles, quantum dots, up-converting phosphor nanoparticles (UCP), fluorescent chemical sensors, DNA, RNA, enzymes, It may be one or more of organic fluorescent molecules and titanium oxide.

The nanotube-synthesized template was immersed in the solution in which the functional material was dispersed or dissolved for 5 minutes to 1 day to allow the solution to diffuse and penetrate into the nanotube, and then taken out of the solution and dried.

The stopper may be formed on the template containing the dried nanotubes by hammering the microbeads.

The method may further comprise selectively etching away the anodized aluminum (AAO) template after sealing the nanotubes.

Phosphoric acid (H 3 PO 4), nitric acid (HNO 3), sulfuric acid (H 2 SO 4), hydrochloric acid (HCl), sodium hydroxide (NaOH), potassium hydroxide (KOH), and the like may be used as the etching solution.

3 is an energy-filtering transmission electron microscope (EF-TEM) of a stoppered nanotube obtained by removing the anodized aluminum oxide (AAO) template.

Referring to Figure 3, it can be seen that the nanotubes formed with a stopper separated from the template.

In another aspect the invention relates to a plugged nanotube made by the method.

The nanotubes have gold nanoparticles, silver nanoparticles, magnetic nanoparticles, quantum dots, up-converting phosphor nanoparticles (UCP), fluorescent chemical sensors, DNA, RNA, enzymes, organic fluorescent molecules, and titanium oxide therein. It may include one or more of the functional material.

Hereinafter, the present invention will be described in detail with reference to Examples, but the features of the present invention are not limited to Examples.

Example 1

An alumina template was prepared by applying a 0.25 mm thick aluminum film with a voltage of 15 V in a 0.3 M oxalic acid solution to produce pores of 80 nm in diameter and 1.5 micron in length through a two-step anodization reaction (first anodization time 10 h, etching). 8h.Secondary polarization time 20min, pore expansion (5% phosphoric acid solution) 40min). The prepared alumina template was immersed in SiCl4 solution for 5 minutes, washed sequentially with hexane, ethanol, water and methanol and dried, and the above procedure was repeated 10 times to generate a silica layer on the base wall of the alumina template to form silica nanotubes. Prepared. After depositing a gold thin film of about 80 nm thickness on the surface of the template containing silica nanotubes by vacuum evaporation, cut it into an appropriate size and place the microtube together with alumina microbeads at a speed of about 1000 rpm. By vibrating and hammering the microbeads, the gold thin film layer was pushed into the nanotube openings to cap the nanotubes. The hammered template was etched in a 25% phosphoric acid solution for 6h and filtered to separate the silica nanotubes from the template.

3 shows an energy-filtering transmission electron microscope (EF-TEM) of the plugged nanotube obtained by removing the anodized aluminum oxide (AAO) template. Referring to FIG. 3, it can be seen that the stopper-shaped nanotubes formed in Example 1 are easy to manufacture, have excellent reproducibility, and metal plugs are inserted into upper portions of the nanotubes to provide a perfect seal.

1 shows a manufacturing method according to an embodiment of the present invention.

Figure 2a shows a scanning electron microscopy (SEM) of the nanotubes after laminating the plug material on the nanotubes.

Figure 2b shows a scanning electron microscopy (SEM) of the nanotubes after hammering the plug material.

3 is an energy-filtering transmission electron microscope (EF-TEM) of a stoppered nanotube obtained by removing the anodized aluminum oxide (AAO) template.

* Description of the main parts of the drawings

10: AAO template 20: nanotube 30: stopper material

40: microbead 100: plugged nanotube

Claims (9)

Forming nanotubes in a plurality of pores formed in the anodized aluminum oxide (AAO) template; Stacking a stopper material on the anodized aluminum oxide (AAO) template and the nanotube; and Sealing the nanotubes by hammering the plug material with microbeads formed of metal Method for producing a stopper formed nanotube comprising a. The method of claim 1, wherein the plug material has a Mohs hardness smaller than that of the microbeads. The method of claim 1, wherein the plug material is gold, silver, nickel, platinum, palladium or alloys thereof, and the microbeads are alumina, silica, titanium oxide, tungsten oxide or alloys thereof. Method of making nanotubes. The method of claim 1, wherein the plug material is a biodegradable resin. The method of claim 1 wherein the step of sealing the nanotubes is Inserting the anodized aluminum oxide template in which the plug material is stacked into a microtube filled with the microbeads; And Vibrating the microtube to hammer the plug material into the microbead. The method of claim 5, wherein said hammering step comprises vibrating said microtube at a speed of 60 to 2000 rpm for 10 minutes to 72 hours. The method of claim 1, wherein the method further comprises the step of forming a nanotube on the anodized aluminum oxide (AAO) template and then filling a functional material inside the nanotube. How to make. The method of claim 1, wherein the method further comprises selectively etching and removing the anodized aluminum oxide (AAO) template after the sealing of the nanotubes. Way. According to any one of claims 1 to 8 as a nanotube formed with a stopper is formed, gold nanoparticles, silver nanoparticles, magnetic nanoparticles, quantum dots, conversion phosphorescent nanoparticles (UCP, up-) inside the nanotubes Converting phosphore nanoparticles), fluorescent chemical sensor, DNA, RNA, enzymes, organic fluorescent molecules and titanium plugs characterized in that it comprises a functional material of at least one of titanium oxide.

Images