KR101079237B1 - Compound having self-assembling property and preparing method thereof, and method for preparing nano structure using the same - Google Patents

Abstract

The present invention relates to a compound having a self-assembling property, a method for preparing the same, and a method for preparing a nanostructure using the same, and more particularly, to a compound represented by the following Formula 1 and a method for producing the same.

[Formula 1]

According to the present invention, a compound having excellent self-assembling properties under a solvent even at room temperature, a method for preparing the same, and a method for preparing a nanostructure using the same can be provided.

Nanostructure, Self-Assembly, Pyrrole Derivatives, Amphiphilic, Peptide Binding

Description

Compound having self-assembling property, method for preparing same, and method for preparing nano structure using the same {Compound having self-assembling property and preparing method etc, and method for preparing nano structure using the same}

The present invention relates to a compound having self-assembling properties, a method for preparing the same, and a method for producing a nanostructure using the same.

Until recently, a great deal of research has been conducted on the preparation of nanotubes from amphiphilic molecules with similar chemical structures.

As one of the methods for preparing nanotubes from amphiphilic molecules having similar chemical structures, Ehud Gazit is an organic solvent 1,1,1,3,3 using hydrophilicity of diphenylalanine and peptide bonds. A method for preparing nanotubes in, 3-hexafluoro-2-propanol (1,1,1,3,3,3-Hexafluoro-2-propanol; HFP) has been studied.

That is, a phenyl group exists at both ends of the molecule, and the nanotube is prepared by using self-assembly in an organic solvent using hydrophobicity of the functional group and hydrophilicity of the peptide bond in the center. The method was attempted (Science, 2003, 300, 625-627, Nature, 2006, 1, 195-200).

It has also recently been found that the conductivity of nanotubes can be used to control alignment in the solution according to the direction of electrical flow (Adv. Mater, 2007, 19. 3924-3927).

However, in the conventional method for producing nanotubes, diphenylalanine, which is a peptide compound, is used. Such a diphenylalanine is not suitable for mass production because the purchase price is high, and when manufacturing nanotubes using the same, the diameter of the tube There is a concern that this is large, there is a problem that not only freezing storage is required, but also the synthesis is not easy.

On the other hand, as a method of forming a pyrrole nanotube using a template, a method of forming a carbon-pyrrole nanotube by attaching pyrrole to a support of a carbon nanotube (Journal of Nanoscience and Nanotechnology, 2007, 7, 3487-3494), Methods for producing pyrrole nanotubes using quantum dots (J. AM. CHEM. SOC., 2005, 127, 496-497) and the like are known.

However, the above methods have a disadvantage in that a separate cost is required according to the manufacture of a template in that a template should be used in manufacturing a nanotube.

Furthermore, unlike the conventional carbon nanotubes, a method of manufacturing π-conjugated polymer nanotubes and nanowires using pyrrole has been developed that facilitates the manufacturing process, easily adjusts electrical characteristics, and has excellent processability (Korea Patent Publication) 2004-0011178) In this case, there was a problem in that, when manufacturing the nanotube, it was necessary to rely on the electrical synthesis method, and in order to realize the shape of the nanotube, a problem in which an electrode having a cylindrical template was used was used. There was this.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and aims to provide a compound having an amphiphilic property including a hydrophobic functional group and a hydrophilic peptide bond, and having excellent self-assembly properties under a solvent even at room temperature.

In addition, another object of the present invention is to provide a method for preparing a compound that is simple in the manufacturing process, can be easily synthesized in a solvent without the addition of a coupling agent, etc., and excellent in reactivity and yield to reduce the manufacturing cost It is.

In addition, another object of the present invention is to provide a method for producing a nanostructure that can easily synthesize a nanostructure by excellent self-assembly reactivity under a solvent even at room temperature.

In addition, another object of the present invention to provide a nanostructure produced using a compound having the self-assembly of the present invention.

The present invention provides a compound represented by the following formula (1) as a means for solving the above problems.

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms,

A ₁ and A ₂ each independently represent a 3 to 7 reduced heterocyclic compound containing at least one nitrogen in the ring.

Moreover, this invention is another means for solving the said subject,

A) preparing a first intermediate by reacting a carboxyl group-containing compound, a condensing agent, and a reaction catalyst represented by Formula 3; B) preparing a second intermediate represented by Formula 4 below; And C) provides a method for producing a compound represented by Formula 1 comprising the step of peptide-linking the first intermediate and the second intermediate.

(3)

[Formula 4]

[Formula 1]

Where

R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms,

A ₁ and A ₂ each independently represent a 3 to 7 reduced heterocyclic compound containing at least one nitrogen in the ring.

In another aspect, the present invention provides a method for producing a nanostructure comprising the step of self-assembling by adding a compound according to the present invention in an organic solvent.

In addition, the present invention provides a nanostructure manufactured by the method for producing a nanostructure of the present invention as another means for solving the above problems.

According to the present invention, an amphiphilic compound capable of exhibiting self-assembly even at room temperature can be prepared, and by adding the compound to an organic solvent, a nanostructure having a small size can be produced by self-assembly of the compound at room temperature. As a result, it is possible to provide a nanostructure having a large surface area and an excellent adsorption amount through a simple process.

Furthermore, in the manufacture of nanostructures, rather than purchasing a separate template or expensive amphiphilic compounds, it is possible to prepare a compound having self-assembly properties by a synthetic method having a better yield at a lower cost, thereby reducing costs The advantage is that the process efficiency can be improved.

Hereinafter, the compound of this invention is demonstrated more concretely.

As described above, the present invention relates to a compound represented by the following formula (1).

In Formula 1, R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, and A ₁ and A ₂ Each independently represents a 3 to 7 reduced heterocyclic compound containing at least one nitrogen in the ring.

The compound has a functional group having hydrophobicity at both ends, as shown in Formula 1, and includes a peptide bond at the stop of the compound.

In this case, the peptide bonds exhibit hydrophilicity, and may exhibit amphiphilicity due to the hydrophilicity of the peptide bonds and the hydrophobicity of the functional groups connected to both ends of the compound, thereby having excellent self-assembly properties. .

On the other hand, in Formula 1, R ₁ and R ₂ may each independently represent an alkylene, alkenylene or alkynylene group having 1 to 8 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, preferably Alkylene, alkenylene or alkynylene groups having 1 to 8 carbon atoms may be represented, and more preferably alkylene, alkenylene or alkynylene groups having 1 to 4 carbon atoms.

When R ₁ and R ₂ are alkylene, alkenylene, or alkynylene groups having 1 to 4 carbon atoms, a region showing hydrophobicity and a region showing hydrophilicity may be balanced to promote self-assembly, such as self-assembly. The properties allow for the formation of more sophisticated structures.

Furthermore, A ₁ and A ₂ may each independently represent a 3 to 7 reduced heterocyclic compound containing nitrogen in the ring, preferably 4 to 6 reducing each containing at least one nitrogen in the ring independently. It may be a heterocyclic compound of, more preferably 5 to 6 reduced heterocyclic compound each containing at least one nitrogen in the ring independently.

Specific examples of more preferable compounds that can be used as A ₁ and A ₂ , wherein A ₁ and A ₂ are each independently aziridine, azirin, azetidine, azolidine, pyrrolidine, pyrroline, pyrrole , Imidazolidine, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, piperidine, pyridine, piperazine, diazine, triazine, tetrazine , Azepine and diazepine may be any one selected from the group consisting of, preferably each independently selected from the group consisting of azolidine, pyrrolidine, pyrroline and pyrrole, more preferably Each may be pyrrole.

Since the pyrrole has excellent electrical conductivity, the nanostructure manufactured by self-assembling it may be more usefully used in various nanomaterial fields that require electrical conductivity as a conductive polymer nanowire.

The compound of the present invention as described above is preferably a compound characterized by the following formula (2).

The compound represented by the formula (2) is a pyrrole derivative, which contains a hydrophilic peptide bond at the stop, and has a pyrrole group connected at both ends thereof, and has excellent amphiphilic properties, and thus is more easily magnetic in room temperature and organic solvent. There is an advantage that the assembly characteristics can be exhibited.

Furthermore, there is an advantage in that excellent self-assembly characteristics can be exhibited at room temperature and in an organic solvent without using a coupling agent.

On the other hand, the present invention comprises the steps of A) preparing a first intermediate by reacting a carboxyl group-containing compound represented by the following formula (3), a condensing agent and a reaction catalyst; B) preparing a second intermediate represented by Formula 4 below; And C) relates to a method for producing a compound represented by Formula 1 comprising the step of peptide-linking the first intermediate and the second intermediate.

Wherein R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 12 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, and A ₁ and A ₂ are each Independently 3 to 7 reduced heterocyclic compounds containing at least one nitrogen in the ring.

Herein, the carboxyl group-containing compound may include all of the compounds represented by Chemical Formula 3, and more preferably, may be a compound represented by the following Chemical Formula 5.

That is, the first intermediate prepared in step A) is preferably a modified pyrrole intermediate obtained by reacting 1-2-carboxyethylpyrrole represented by the formula (5) with a condensing agent and a reaction catalyst.

As described above, when the first intermediate is manufactured using the 1-2-carboxyethylpyrrole represented by Chemical Formula 5, the reactivity is improved, so that the reaction can be performed at room temperature, and the yield may be greatly improved. .

In general, the compounds having self-assembly properties are often reacted at high temperature, the compound according to the present invention has the advantage that the nano-structure can be more easily prepared because of excellent reactivity at room temperature.

That is, the compound according to the present invention may cause a self-assembly reaction even at a temperature of 50 ° C. or less, and preferably, a reaction even at a temperature of 25 to 30 ° C.

In addition, the condensing agent is used to control the reaction in the condensation reaction with the carboxyl group-containing compound as described above, but may include all condensing agents that can be used during such condensation reaction, preferably 1-cyclohexyl-3- (morpholinoethyl) carbodiimide (CMC), diisopropyl carbodiimide (DIC), 1,1'-carbonyldiimidazole (CDI), 1,3-dicyclohexyl One or more selected from the group consisting of carbodiimide (DCC) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC), more preferably 1-ethyl-3 -(3-dimethylaminopropyl) carbodiimide hydrochloride can be used.

The 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride shows water solubility and has the advantage of easy separation after the reaction. In the method for preparing a compound according to the present invention, the preparation of a first intermediate It may be more usefully used as a condensing agent used in the.

In addition, the reaction catalyst is preferably one or more selected from the group consisting of 4-dimethylaminopyridine, N-hydroxysuccinimide and 4-pyrrolidinopyridine, and more preferably N-hydroxysuccinimide. .

Since the N-hydroxysuccinimide reacts with the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride to form an amide bond, the N-hydroxysuccinimide is used according to the present invention to modify the carboxyl group-containing compound according to the present invention. The first intermediate used in the preparation of the compound can be prepared.

However, the reaction catalyst may also include all compounds that can act as a catalyst for promoting the reaction, but is not limited to the materials exemplified above.

On the other hand, the first intermediate is preferably obtained by reacting 10 parts by weight of the carboxyl group-containing compound, 10 to 30 parts by weight of the condensing agent and 10 to 20 parts by weight of the reaction catalyst.

Thus, the first intermediate as described above is preferably a compound represented by the following formula (6).

Since the compound represented by Chemical Formula 6 has a NHS-ester group at the terminal, it may react with the amine group of the second intermediate to cause a peptide binding reaction, thereby preparing a pyrrole derivative having amphipathic and self-assembled properties. have.

On the other hand, the second intermediate is preferably a compound represented by the following formula (7).

The second intermediate is a structure in which CH ₂ CH ₂ CH ₂ NH ₂ is bonded to a nitrogen atom of a pyrrole group, and when such a pyrrole intermediate is used in the reaction with the first intermediate, it may exhibit better reactivity.

On the other hand, the present invention relates to a method for producing a nanostructure comprising the step of self-assembling by adding the compound according to the invention as described above in an organic solvent.

That is, as described above, the compound according to the present invention can produce nanostructures by self-assembly by simply adding a compound having excellent self-assembly properties in an organic solvent in an organic solvent even at room temperature. In manufacturing, there is no need to use a conventional template or expensive compounds, there is an advantage that can be produced nanostructures in a short time at a low cost.

Herein, the organic solvent may include all of various solvents in which the compound according to the present invention may be self-assembled, but for example, 1,1,1,3,3,3-hexafluoro-2-propanol (1, 1, 1, 3, 3, 3-hexafluoro-2-propanol), methanedithione (CS ₂ ), carbon tetrachloride (CCl ₄ ), benzene, toluene and the like.

As such, a method of manufacturing a nanotube according to an embodiment of the present invention is shown in FIG. 1.

The present invention also relates to a nanostructure produced according to the method of the present invention.

That is, the nanostructures prepared according to the method described above can be easily manufactured at a lower cost, and further show excellent electrical conductivity, and can form nanotubes having a relatively small diameter. There is an advantage that can be utilized.

In addition, the nanostructure prepared as described above may be made of a bundle structure, a tube structure or a sheet structure according to the composition of the compound to be self-assembled, may form a composite.

That is, the nanostructures of various structures can be prepared using the self-assembly of the compounds according to the present invention. Preferably, the nanostructures may be nanotubes.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

Preparation Example 1 Synthesis of First Intermediate

A first intermediate used to prepare a compound according to an embodiment of the present invention was prepared by the following method.

First, 4.77 ml (5 g) of 1-2-cyanoethyl pyrrole (1- (2-cyanoethyl) pyrrole) was added to 12 ml of 6.7 M of KOH (potassium hydroxide), and nitrogen was purged. Here, the mixed solution was heated for 4 hours 30 minutes while stirring at a temperature of 200 ℃, and then cooled at room temperature.

After cooling the mixed solution, 8M HCl (hydrogen chloride) was added to acidify the pH of the mixed solution to 3. The resulting compound was extracted five times using 50 ml of Ether while maintaining the pH of the mixture at 3, and then the ether was removed by evaporation with a rotary evaporator.

After the ether was removed, the obtained dark brown liquid was crystallized at room temperature to obtain a basic colored crystal. The crystals thus obtained were further added to N-heptane, heated at 62 ° C. to melt, and cooled to obtain needle-free colorless recrystallized.

It was then filtered to remove the used N-heptane and dried in a vacuum oven to give a carboxyl-modified pyrrole intermediate (1- (2-carboxyethyl) pyrrole).

The pyrrole intermediate (1- (2-carboxyethyl) pyrrole), EDC (1-Ethyl-3- [3-dimethylaminopropyl] carboimide hydrochloride) and NHS (N-hydrosuccinimide) were each 10 ml of water in a weight ratio of 2: 4: 3. After dissolving in and reacting, the mixture was filtered and dried to obtain py-NSE. Py-NSE prepared above was confirmed under FT-IR and shown in FIG. 2.

Preparation Example 2 Synthesis of Second Intermediate

A second intermediate used to prepare a compound according to an embodiment of the present invention was prepared by the following method.

To 33.75 ml of diethyl ether purged with nitrogen for 30 minutes, 3.75 ml of 1.0 M lithium aluminum hydride (LiAlH ₄ ) was introduced into a syringe.

A solution of 0.488 ml of 1-2-cyanoethylpyrrole in 3.75 ml of diethyl ether was added to the solution, followed by stirring at 300 rpm for 2 hours and 30 minutes while refluxing with cooling water at a temperature of 40 ° C.

Thereafter, 0.425 ml of DI water, 0.425 ml of 15% sodium hydroxide (NaOH), and 1.275 ml of DI water were sequentially added at room temperature, and then reacted for 2 hours while refluxing with cooling water at a temperature of 40 ° C. .

This gave a yellow, modified 1-3-aminopropylpyrrole solution, which was filtered using Celite, and the ether was removed using a rotary concentrator at a temperature of 40 ° C. to have amine groups. Modified 1-3-aminopropylpyrrole was obtained.

The 1-3-aminopropylpyrrole was confirmed through the nuclear magnetic resonance device, and it is shown in FIG.

Example 1 Synthesis of Compound Having Self-Assembly Properties

Compounds according to one embodiment of the present invention were prepared in the following manner.

After dissolving py-NSE prepared in Preparation Example 1 in water, 1-3-aminopropylpyrrole prepared in Preparation Example 2 was added and stirred at least one day at low temperature to chemically bond the two materials.

Ether was added to the obtained solution in a volume ratio of 1: 1, and the mixture was separated. Thus, the intermediate layer, which appeared milky, was extracted from the resultant separated into three layers, and the ether was evaporated at room temperature.

The pyrrole derivative thus obtained was confirmed using a nuclear magnetic resonance apparatus, which is shown in FIG.

Referring to FIG. 4, the NH ₂ peak disappeared and the amide peak appeared, indicating that a pyrrole derivative having self-assembly was synthesized.

The self-assembly photograph of the pyrrole derivatives synthesized accordingly was confirmed through a transmission electron microscope, which is shown in FIG. 5.

1 is a schematic diagram schematically showing the synthesis of a compound according to an embodiment of the present invention and a method of manufacturing a nanostructure using the same,

Figure 2 is a first intermediate used in the preparation of the compound according to an embodiment of the present invention, showing the FT-IR peak of py-NSE,

Figure 3 is a second intermediate used in the preparation of the compound according to an embodiment of the present invention, it shows a peak of NMR of 1-3-aminopropylpyrrole,

Figure 4 shows the peak of NMR of the compound according to an embodiment of the present invention,

5 is a photograph of a cylindrical magnetic assembly manufactured using a compound according to an embodiment of the present invention.

Claims (19)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 4 carbon atoms, A ₁ and A ₂ each independently represent any one selected from the group consisting of azolidine, pyrrolidine, pyrroline and pyrrole. delete delete delete delete The method of claim 1, And A ₁ and A ₂ are each pyrrole. The method of claim 1, A compound represented by the following formula (2). [Formula 2]

A) preparing a first intermediate by reacting a carboxyl group-containing compound, a condensing agent, and a reaction catalyst represented by Formula 3; B) preparing a second intermediate represented by Formula 4 below; And C) A method for preparing a compound represented by Formula 1 comprising the step of peptide-linking the first intermediate and the second intermediate: (3)

[Formula 4]

[Formula 1]

Where R ₁ and R ₂ each independently represent an alkylene, alkenylene or alkynylene group having 1 to 4 carbon atoms, A ₁ and A ₂ each independently represent any one selected from the group consisting of azolidine, pyrrolidine, pyrroline and pyrrole. The method of claim 8, Carboxyl group-containing compound is a method for producing a compound, characterized in that the compound represented by the formula (5). [Chemical Formula 5]

The method of claim 8, Condensing agents include 1-cyclohexyl-3- (morpholinoethyl) carbodiimide, diisopropyl carbodiimide, 1,1'-carbonyldiimidazole, 1,3-dicyclohexyl carbodiimide and 1- A method for producing a compound, characterized in that at least one member selected from the group consisting of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. The method of claim 8, A condensation agent is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. The method of claim 8, The reaction catalyst is at least one selected from the group consisting of 4-dimethylaminopyridine, N-hydroxysuccinimide and 4-pyrrolidinopyridine. The method of claim 8, Method for producing a compound, characterized in that the reaction catalyst is N-hydroxysuccinimide. The method of claim 8, The first intermediate is obtained by reacting 10 parts by weight of the carboxyl group-containing compound, 10 to 30 parts by weight of the condensing agent and 10 to 20 parts by weight of the reaction catalyst. The method of claim 8, Method for producing a compound, characterized in that the first intermediate is a compound represented by the following formula (6). [Formula 6]

The method of claim 8, Method for producing a compound, characterized in that the second intermediate is a compound represented by the following formula (7). [Formula 7]

A method for producing a nanostructure comprising self-assembling by adding a compound according to claim 1 in an organic solvent. The method of claim 17, The organic solvent is a method for producing a nanostructure, characterized in that selected from the group consisting of 1,1,1,3,3,3-hexafluoro-2-propanol, methanedithione, carbon tetrachloride, benzene and toluene. Nanostructure prepared according to the method of claim 17.

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