Patent Grant
10486971
The present invention relates to a one-dimensional material, and more particularly, to a scroll.
Two-dimensional materials such as graphene have different thermal, mechanical and electrical characteristics from three-dimensional bulk materials. Specifically, the two-dimensional materials are known to have excellent mechanical strength, intensity and flexibility, and also have excellent electrical and thermal conductivities. Due to the excellent characteristics of such a two-dimensional material, the two-dimensional material is widely applied to an energy storage device, an energy conversion device, a sensor, a catalyst, and a bio micro electro mechanical system (bio MEMS).
Meanwhile, since a carbon nanotube, which is a one-dimensional material corresponding to an allotrope of graphene, has excellent thermal, mechanical and electrical characteristics, it is also applied in various fields like the two-dimensional material.
Research on the preparation of a composite structure including desired various materials inside the nanotube is progressing. A carbon nanotube composite material has been made by adding a desired material such as fullerene (Brian W. Smith, Marc Monthioux, David E. Luzzi, Encapsulated C60 in carbon nanotubes, Nature, VOL 396, 26 Nov. 1998), an organic material (TAISHI TAKENOBU et al., Stable and controlled amphiphilic doping by encapsulation of organic molecules inside carbon nanotubes, Nature Materials, VOL 2, OCTOBER, 2003), a metal (Jean-Philippe et al., Selective Deposition of Metal Nanoparticles Inside or Outside Multiwalled Carbon Nanotubes, ACSNano, VOL. 3, NO. 8, 2081-2089, 2009) into a carbon nanotube. However, it was not easy to prepare the nanotube with open ends, and to remove a desired material after addition thereof.
Therefore, an object to be solved by the present invention is to provide a method for forming a one-dimensional scroll by inducing the roll-up of a two-dimensional material, and the one-dimensional scroll formed thereby.
Technical problems of the present invention are not limited to those described above, and other technical problems that have not been described will be fully understood to those of ordinary skill in the art from the descriptions that will be described below.
One aspect of the present invention provides a scroll composite. The scroll composite includes a two-dimensional material scroll with open ends. An amphiphilic substance is disposed inside the scroll.
The two-dimensional material may be a single substance selected from the group consisting of graphene, graphene oxide, boron nitride, boron carbon nitride (BCN), tungsten oxide (WO3), tungsten sulfide (WS2), molybdenum sulfide (MoS2), molybdenum telluride (MoTe2), and manganese oxide (MnO2), or a composite substance including a stack of two or more thereof.
The amphiphilic substance may be a surfactant, a bile acid, a bile acid salt, a hydrate of a bile acid salt, a bile acid ester, a bile acid derivative, or a bacteriophage.
The amphiphilic substance may be in a self-assembled structure. Hydrophilic portions of the amphiphilic substances may be exposed at the exterior of the self-assembled structure. The self-assembled structure may have a spherical, rod-shaped or fiber-shaped structure.
The self-assembled structure of the amphiphilic substance may include core particles and one or more shells including the amphiphilic substances self-assembled on the core particle. A hydrophilic portion of the amphiphilic substance may be exposed at the exterior of the self-assembled structure of the amphiphilic substance. The core particle may have a spherical or rod-shaped structure. The core particle may be a metal particle, a metal oxide particle, or a bacteriophage.
One aspect of the present invention provides a two-dimensional material scroll. The two-dimensional material scroll has a structure in which a two-dimensional material is rolled up, and which has van der Waals interactions between adjacent two-dimensional material sheets and has open ends. The two-dimensional material scroll may be a hollow scroll having an empty inside.
One aspect of the present invention provides a method for preparing a two-dimensional material scroll. First, a two-dimensional material is provided. The two-dimensional material is scrolled by providing an amphiphilic substance having a hydrophilic portion and a hydrophobic portion on the two-dimensional material. As a result, the amphiphilic substance is disposed inside the scrolled structure, thereby forming a scroll composite.
The two-dimensional material may be dispersed in a solvent, thereby providing a two-dimensional material dispersion. The providing of the amphiphilic substance may be mixing an amphiphilic substance solution prepared by dissolving the amphiphilic substance in a solvent with the two-dimensional material dispersion. The amphiphilic substance solution may be heated before being mixed with the two-dimensional material dispersion. In addition, the heated amphiphilic substance solution may be cooled before being mixed with the two-dimensional material dispersion.
The amphiphilic substance solution may include core particles.
At least a part of the amphiphilic substance may be removed by solvent treatment and/or thermal treatment on the scroll composite, thereby forming a hollow scroll. The solvent may be one which dissolves the amphiphilic substance. The thermal treatment may be performed at 200 to 800° C.
As described above, according to the present invention, a one-dimensional scroll may be easily formed by inducing the roll-up of a two-dimensional material using an amphiphilic substance. Also, the one-dimensional scroll may be provided.
Hereinafter, to more fully explain the present invention, exemplary embodiments according to the present invention will be described in further detail with reference to the accompanying drawings. However, the present invention may be embodied in different forms and should not be understood as being limited to the examples, which will not be described herein.
Referring to
The two-dimensional material 30 may be a composite material including a single substance selected from the group consisting of graphene, graphene oxide, boron nitride, boron carbon nitride (BCN), tungsten oxide (WO3), tungsten sulfide (WS2), molybdenum sulfide (MoS2), molybdenum telluride (MoTe2), and manganese oxide (MnO2), or a composite material including a stack of two or more thereof. The composite material may be one in which boron nitride, boron carbon nitride or molybdenum sulfide is stacked on graphene, or one in which molybdenum sulfide is stacked on boron nitride.
Edges of such a two-dimensional material 30 have lower stability due to higher surface energy than an in-plane region, and thus enables easy oxidation.
The two-dimensional material 30 may be dispersed in a solvent, thereby preparing a two-dimensional material dispersion. Specifically, the two-dimensional material dispersion may be obtained by dispersing two-dimensional material powder in a solvent by mechanical stirring or sonication, and then performing centrifugation. The solvent may be one selected from the group consisting of water, methanol, ethanol, isopropyl alcohol, toluene, benzene, hexane, heptane, m-cresol, ethyl acetate, carbon disulfide, dimethylsulfoxide, dichloromethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, tetrahydrofuran, dimethylacetamide, N-methylpyrrolidone, and acetic acid, or a combination of two or more thereof. The solvent may be suitably selected depending on the two-dimensional material to easily disperse the two-dimensional material.
An amphiphilic substance 10 may be provided on the two-dimensional material 30. Specifically, the amphiphilic substance 10 may be added into the solvent in which the two-dimensional material 30 is dispersed, or an amphiphilic substance solution prepared by dissolving the amphiphilic substance 10 in a solvent may be mixed with the two-dimensional material dispersion. In addition, the amphiphilic substance solution may be heated before being mixed with the two-dimensional material dispersion. In this case, the amphiphilic substance solution may be cooled while being mixed with the two-dimensional material dispersion at room temperature, and thus the amphiphilic substance 10 may be easily self-assembled at an edge of the two-dimensional material 30.
In the amphiphilic substance solution, the amphiphilic substance may be contained, for example, at a concentration of 0.001 g/mL to 1 g/mL, but the present invention is not limited thereto. However, according to the concentration of the amphiphilic substance, an amount of scroll composites 40 (
The solvent used in the amphiphilic substance solution may be one selected from the group consisting of water, methanol, ethanol, isopropyl alcohol, toluene, benzene, hexane, heptane, m-cresol, ethyl acetate, carbon disulfide, dimethylsulfoxide, dichloromethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, tetrahydrofuran, dimethylacetamide, N-methylpyrrolidone, dimethylformamide and acetic acid, or a combination of two or more thereof, and may be the same as or different from that used for the two-dimensional material dispersion.
The amphiphilic substance 10 may be a substance having both of a hydrophilic portion 10a and a hydrophobic portion 10b in one molecule. Specifically, the amphiphilic substance 10 may be an organic material such as a surfactant, a bile acid, a bile acid salt, a hydrate of a bile acid salt, a bile acid ester, a bile acid derivative, or a bacteriophage.
The surfactant may include one or more compounds selected from the group consisting of sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, sodium laureth sulfate, alkyl benzene sulfonate, cetyl trimethylammonium bromide (CTAB), hexadecyl trimethyl ammonium bromide, an alkyltrimethylammonium salt, cetylpyridinium chloride (CPCl), polyethoxylated tallow amine (POEA), benzalkonium chloride (BAC), benzethonium chloride (BZT), dodecyl betaine, dodecyl dimethylamine oxide, cocamidopropyl betaine, alkyl poly(ethylene oxide), a poloxamer, a poloxamine, alkyl polyglucoside, cetyl alcohol, sodium deoxycholate, cocamide MEA, cocamide DEA, sorbitan ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyethyelene glycol hydroxystearate, polyoxyethylene glycolated natural or hydrogenated castor oil, a polyoxyethylene-polyoxypropylene copolymer, a synthetic vitamin E derivative, polyoxyethylene alkyl ester, fatty acid microgol glyceride, polyglyceryl fatty acid ester, and a silicone-based surfactant. The one or more compounds may include one or more types of compounds, or the same type of two or more compounds.
The bile acid may be, for example, represented by Formula 1 below.
In Formula 1, R1 and R2 may each be independently —H or —OH, R3 may be —(CONH—(CH2)n1)n2—Y1, n1 may be 1 or 2, n2 may be 1 or 0, and Y1 may be —COOH or —SO3H. In one example, R1, R2, and R3 may be the same as described in Table 1.
Another example of the bile acid may be dehydrocholic acid, hyodeoxycholic acid, or ursodeoxycholic acid.
The bile acid salt may be a metal salt of the bile acid, and specifically, a bile acid sodium salt. In one example, the bile acid salt may be sodium glycochenodeoxycholate, sodium taurochenodeoxycholate, sodium taurocholate, sodium dehydrocholate, or sodium deoxycholate.
Also, the hydrate of a bile acid salt may be a hydrate of the bile acid metal salt, and specifically, a hydrate of the bile acid sodium salt. In one example, the hydrate of a bile acid salt may be sodium taurocholate hydrate or sodium cholate hydrate.
The bile acid ester may be hyodeoxycholic acid methyl ester.
The bile acid derivative may be represented by Formula 2 below.
In Formula 2, n is 0, 1 or 2, and R4 to R7 are each independently a group represented by Formula 3.B1
m
L1
nG1 [Formula 3]
In Formula 3, B1 is one group selected from the group consisting of
L1 is a linker of —W1—, -Q1-, -Q2-W2—, —W3-Q3-W4—, or —W5-Q4-W6-Q5-Q6-, W1, W2, W3, W4, W5, and W6 are each independently
a1 to a3 are each an integer of 1 to 4, Q1, Q2, Q3, Q4, Q5, and Q6 are each independently
and
G1 is a group represented by
In addition, m is 0 or 1, n is 0 or 1, and when both of m and n are 0, G1 is directly linked without B1 and L1.
In one example, R4, R5, and R6 may each be independently —H, —OH, —SO3H, —OSO3H, or ═O, and R7 may be a group represented by Formula 3.
The bile acid derivative may be any one of the bile acid derivatives of Formulas 4 to 20.
The bile acid includes an α-face exhibiting hydrophilicity since at least one —OH and a —COOH or —SO3H group are exposed, and a β-face exhibiting hydrophobicity since —CH3 groups are exposed, thereby exhibiting amphiphilicity. Also, the bile acid derivative includes an α-face exhibiting hydrophilicity since G1 groups of Formula 3 are exposed and a β-face exhibiting hydrophobicity since —CH3 groups are exposed, resulting in exhibiting amphiphilicity.
The bacteriophage is known to include a protein part and hydrophobic tails. Therefore, the bacteriophage may be amphiphilic. The bacteriophage may be a rod-shaped filamentous bacteriophage. The filamentous bacteriophage is known to have a hydrophilic rod disposed in the center due to a residue such as a carboxyl group or amine group, and hydrophobic tails disposed at both ends. In one example, the bacteriophage may be at least one selected from the group consisting of T1, T2, T3, T4, T5, T6, T7, M13, MS2, fd, f1 and P22.
The hydrophilic portion 10a of such an amphiphilic substance 10 may be bound to edges having high surface energy, particularly, an edge having the highest surface energy, of the two-dimensional material 30. Specifically, an edge of the two-dimensional material 30 may be bound to the hydrophilic portion 10a of the amphiphilic substance 10 by a surface interaction 21. The surface interaction may be a hydrophilic-hydrophilic interaction, an interaction between a Lewis acid and a Lewis base, or a hydrogen bond. Here, the hydrophobic portions 10b of the amphiphilic substances 10, wherein the amphiphilic substances 10 are adjacent to each other and bound to the edges of the two-dimensional material 30, may be bound to each other by a force 22 such as a van der Waals force. Therefore, the amphiphilic substance 10 may be self-assembled to the edge of the two-dimensional material 30.
Referring to both
Once the scrolling of the two-dimensional material 30 is initiated, the scrolling is accelerated by van der Waals interactions 25, for example, a π-π interaction, between in-plane regions of the two-dimensional material 30, and thus the two-dimensional material 30 may be changed into a scrolled structure, that is, a roll shape. As a result, a scroll composite 40, in which the amphiphilic substance 10 is disposed inside, specifically, in the center of the scrolled structure of the two-dimensional material, may be formed. The two-dimensional material scroll, that is, the scroll composite 40 may have a one-dimensional structure, which is rod shaped or fiber shaped, and have open ends.
The amphiphilic substance 10 may remain in the scroll composite 40. As the size, shape or amount of the amphiphilic substance 10 is adjusted, the inner size of the scroll composite 40 is able to be adjusted.
Referring to
Etching may be enhanced by adding thermal treatment while using the solvent.
The solvent, which is a material capable of selectively dissolving only the amphiphilic substance 10, may be at least one selected from the group consisting of water, methanol, ethanol, isopropyl alcohol, toluene, benzene, hexane, heptane, m-cresol, ethyl acetate, carbon disulfide, dimethylsulfoxide, dichloromethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, tetrahydrofuran, dimethylacctamide, N-methylpyrrolidone, dimethylformamide and acetic acid, and a solvent treatment time may be 1 to 24 hours, or several days, but the present invention is not limited thereto.
Meanwhile, the scroll composite may not be unrolled in the solvent by the van der Waals interactions 25 between adjacent two-dimensional material sheets.
To the extent that a shape of the scroll is not deformed, a temperature of the thermal treatment may be, but is not particularly limited to, for example, 100 to 800° C., 100 to 700° C., 100 to 600° C., 100 to 500° C., 200 to 800° C., 200 to 700° C., 200 to 600° C., 200 to 500° C., 300 to 800° C., 300 to 700° C., 300 to 600° C., 300 to 500° C., 400 to 800° C., 400 to 700° C., 400 to 600° C., or 400 to 500° C., 500 to 800° C., 500 to 700° C., or 500 to 600° C., the treatment time may be, but is not limited to, 0.1 to 10 hours. When the thermal treatment is performed in a gas atmosphere, a gas may be, for example, argon, nitrogen, etc. Also, the inert gas may be provided at a rate of, for example, approximately 1 to 10 cc/min.
The thermal treatment may be, but is not limited to, induction heating, radiant heat, laser, IR, microwave, plasma, UV or surface plasmon heating.
Referring to
The hydrophilic rod 10a of such a bacteriophage 10 may be bound to edges having high surface energy, particularly, an edge having the highest surface energy among these edges, of the two-dimensional material 30. Specifically, an edge of the two-dimensional material 30 may be bound to the hydrophilic rod 10a of the bacteriophage 10 by a surface interaction 21. The hydrophobic tails 10b of the bacteriophage 10 may have an interaction 23 with an in-plane region of the two-dimensional material 30 by van der Waals forces. Such an interaction may initiate scrolling of the two-dimensional material 30. However, even when there is no such interaction 23, it is assumed that the scrolling of the two-dimensional material 30 may be initiated only by the surface interaction 21 between an edge of the two-dimensional material 30 and the hydrophilic rod 10a of the bacteriophage 10. After the scrolling of the two-dimensional material 30 is initiated, the scrolling is accelerated by the van der Waals interactions 25 (
Referring to
In such self assemblies M1 and M2, hydrophilic portions 10a of the amphiphilic substance 10 may be exposed to the outside. Meanwhile, the shape of such self assemblies M1 and M2 may be determined by a solvent in the amphiphilic substance solution.
Meanwhile, the diameter and/or length of the self assemblies M1 and M2 may be changed depending on the concentration, heating temperature, cooling temperature, and maintaining time of the amphiphilic substance in the amphiphilic substance solution. To this end, the concentration of the amphiphilic substance in the amphiphilic substance solution may be approximately 0.001 g/L to 1 g/L. The heating temperature may be 30 to 200° C. The cooling temperature may be approximately −196 to 25° C. Also, the maintaining time may be 0.5 to 24 hours.
The hydrophilic portions 10a of the amphiphilic substance, which are exposed to the outside, of such self assemblies M1 and M2 may be bound to edges of the two-dimensional material 30 having high surface energy, particularly, an edge having the highest surface energy. Specifically, an edge of the two-dimensional material 30 may be bound to the hydrophilic portions 10a of the amphiphilic substance 10 by surface interactions 21. Meanwhile, the hydrophobic portions 10b of the amphiphilic substance 10 may be exposed in a region of the self assemblies M1 and M2, in which the amphiphilic substance 10 is disposed at a very low density, and the exposed hydrophobic portions 10b may have interactions 23 with an in-plane region of the two-dimensional material 30 by van der Waals forces. Such interactions may initiate scrolling of the two-dimensional material 30. However, even when there is no interaction 23, it is assumed that the scrolling of the two-dimensional material 30 may be initiated only by the surface interactions 21 between an edge of the two-dimensional material 30 and the hydrophilic portions 10a of the amphiphilic substance 10.
Referring to
Afterward, a hollow scroll 50 (of
Referring to
The metal particles may be Au, Ag, Fe, Al, Cu, Co, Ni, W, Zn, Mo, Ti, Ru, Pd, Ge, Pt, Li, Si, or an alloy particle of two or more thereof, and may have a diameter of 1 nm to 10 μm. The metal oxide particles may be Al(OH)3, Al2O3, MnO, SiO2, ZnO, Fe2O3, Fe3O4, Li4Ti5O12, LiNi0.5Mn1.5O4 or TiO2 particles, and may have a diameter of 1 nm to 10 μm. When the metal particles or metal oxide particles have a rod shape, the particle may have a length of 1 nm to 10 μm.
The providing of the self assemblies C1 and C2 of the amphiphilic substance on the two-dimensional material 30 may be performed by stirring the amphiphilic substance 10 and the core particles added to a solvent, thereby preparing an amphiphilic substance solution, and mixing the amphiphilic substance solution with a two-dimensional material dispersion.
The metal particles, the metal oxide particles, and the bacteriophages 15 and 17 may have a hydrophilic surface, and thus hydrophilic portions 10a of the amphiphilic substance 10 may be self-assembled on the hydrophilic substance, thereby forming a first shell S1. On the surface of the first shell S1, hydrophobic portions 10b of the amphiphilic substance 10 may be exposed, and hydrophobic portions 10b of the amphiphilic substance 10 may be self-assembled again on the surface of the first shell S1, thereby forming a second shell S2. The hydrophilic portion 10a may be exposed at the surface of the second shell S2. However, since the second shell S2 may have the amphiphilic substance 10 disposed at a very low density, compared with the first shell S1, both of the hydrophilic portion 10a and the hydrophobic portion 10b may be exposed to the surfaces of the self assemblies C1 and C2 of the amphiphilic substance.
The hydrophilic portion 10a exposed at the surface of the self assemblies C1 and C2 of the amphiphilic substance may be bound to edges of the two-dimensional material 30 having high surface energy, particularly, an edge having the highest surface energy. Further, the hydrophobic portions 10b exposed at the surfaces of the self assemblies C1 and C2 of the amphiphilic substance may have interactions 23 with an in-plane region of the two-dimensional material 30 by van der Waals forces. Such an interaction may initiate scrolling of the two-dimensional material 30. However, even when there is no such interaction 23, it is assumed that the scrolling of the two-dimensional material 30 may be initiated only by surface interactions 21 between an edge of the two-dimensional material 30 and the hydrophilic portions 10a of the amphiphilic substances 10.
After the scrolling of the two-dimensional material 30 is initiated, the scrolling is accelerated by van der Waals interactions 25 (of
In addition, the inner size, for example, the inner diameter of the scroll composite 40 (of
Afterward, a hollow scroll 50 (of
Hereinafter, exemplary examples are provided to help in understanding the present invention. However, the following examples are merely provided to help in understanding the present invention, not to limit the present invention by the following examples.
1.5 g of graphene, which is a two-dimensional material, was put into a solvent shown in Table 2 or 6, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, following sonication for 30 minutes, the dispersion was centrifuged at 4400 rpm for 30 minutes, thereby obtaining a graphene dispersion, which is a supernatant.
Meanwhile, any one of the amphiphilic substances such as bile acid derivatives represented by Formulas 4 to 8 (Preparation Examples 1 to 6), sodium dodecyl sulfate (Preparation Example 7), lauroyl microgol glyceride (Preparation Example 8), sodium cholate hydrate as a hydrate of a bile acid salt (Preparation Example 9), deoxycholic acid as bile acid (Preparation Example 9), bacteriophages T1, M13, and fd (Preparation Examples 11 to 13), or bile acid derivatives represented by Formulas 13 to 15 (Preparation Examples 66 to 68) was put into a solvent shown in Table 2 or 6 with a weight shown in Table 2 or 6, thereby preparing an amphiphilic substance solution. Afterward, the resulting solution was heated to a temperature shown in Table 2 or 6.
Afterward, in Preparation Examples 2 to 4, 6 to 8, 10 to 13, and 66, the amphiphilic substance solution may be maintained at a temperature shown in Table 2 or 6 for a time shown in Table 2 or 6 to recrystallize, self-assemble or micellize the amphiphilic substance.
After the graphene dispersion was mixed with the amphiphilic substance solution, the resulting mixed solution was maintained at a temperature shown in Table 2 or 6 for a time shown in Table 2 or 6. Afterward, graphene scroll composites including the amphiphilic substance inside a graphene scroll were obtained by filtering with a PTFE membrane.
A graphene dispersion was obtained using the same method as described in Preparation Example 1, except that 1.5 g of graphene was put into methanol.
A bile acid derivative (Formula 4) as an amphiphilic substance, and TiO2 particles (diameter: 20 nm, R&D Korea) as metal oxide particles were added to methanol in a weight ratio of 97:3, thereby preparing a solution having a sum concentration of 2.0 wt %, and the resulting solution was stirred for 5 hours, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 65° C., and maintained at 11° C. for 3 hours.
Subsequently, the graphene dispersion was mixed with the amphiphilic substance solution, and then the resulting mixture was maintained at 60° C. for 5 hours. As a result, a graphene scroll composite including a self assembly of the amphiphilic substance inside a graphene scroll was obtained.
A graphene dispersion was obtained using the same method as described in Preparation Example 1, except that 1.5 g of graphene was added to heptane.
A bile acid derivative of Formula 4 as an amphiphilic substance and a bacteriophage P22 were added to heptane in a weight ratio of 80:20, thereby preparing a solution having a sum concentration of 3.0 wt %, and the resulting solution was stirred for 1 hour, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 90° C.
The graphene dispersion was mixed with the amphiphilic substance solution, and then maintained at 180° C. for 3 hours. As a result, a graphene scroll composite including a self assembly of the amphiphilic substance inside a graphene scroll was obtained.
A graphene dispersion was obtained using the same method as described in Preparation Example 1, except that 1.5 g of graphene was added to carbon disulfide.
Deoxycholic acid as an amphiphilic substance and a Fe3O4 particles as metal oxide particles were added to carbon disulfide in a weight ratio of 60:40, thereby preparing a solution having a sum concentration of 5 wt %, and the resulting solution was stirred for 3 hours, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 110° C., and maintained at 0° C. for 4 hours.
The graphene dispersion was mixed with the amphiphilic substance solution, and maintained at 10° C. for 6 hours. As a result, a graphene scroll composite including a self assembly of the amphiphilic substance inside a graphene scroll was obtained.
A graphene dispersion was obtained using the same method as described in Preparation Example 1, except that 1.5 g of graphene was added to dichloromethane.
A sodium dodecyl sulfate as an amphiphilic substance and Ag particles (diameter: 1 μm, R&D Korea) as metal particles were added to dichloromethane in a weight ratio of 90:10, thereby preparing a solution having a sum concentration of 2.0 wt %, and the resulting solution was stirred for 1 hour, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 40° C., and maintained at −4° C. for 5.5 hours.
The graphene dispersion was mixed with the amphiphilic substance solution, and maintained at room temperature for 1 hour. As a result, a graphene scroll composite including a self assembly of the amphiphilic substance inside a graphene scroll was obtained.
1.5 g of boron nitride as a two-dimensional material was added to 5 ml of ODCB, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, following sonication for 30 minutes and centrifugation at 4400 rpm for 30 minutes, a boron nitride dispersion, which is a supernatant, was obtained.
Meanwhile, 0.02 mmol of the bile acid derivative of Formula 4 as an amphiphilic substance was dissolved in 1 ml of ODCB, thereby preparing an amphiphilic substance solution. The amphiphilic substance solution was heated to 60° C.
The boron nitride dispersion was mixed with the heated amphiphilic substance solution, and maintained at room temperature for 24 hours. As a result, a boron nitride dispersion scroll composite including a self assembly of the amphiphilic substance inside a boron nitride dispersion scroll was obtained.
0.002 mmol of the bile acid derivative of Formula 4 as an amphiphilic substance was dissolved in 1 ml of ODCB, thereby preparing an amphiphilic substance solution. The amphiphilic substance solution was heated to 60° C. Afterward, the heated amphiphilic substance solution was maintained at room temperature for 24 hours. Except the above-described process, a boron nitride scroll composite including the amphiphilic substance inside a boron nitride scroll was obtained using the same method as used in Preparation Example 18.
1.5 g of boron nitride as a two-dimensional material was added to a solvent shown in Table 3 or 6, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, following sonication for 30 minutes and centrifugation at 4400 rpm for 30 minutes, a boron nitride dispersion as a supernatant was obtained.
Meanwhile, any one of the amphiphilic substances such as an N-hexadecyltrimethylammonium salt (Preparation Example 20), benzalkonium chloride (Preparation Example 21), a bile acid derivative represented by Formula 7 (Preparation Example 22), a bile acid derivative represented by Formula 8 (Preparation Example 23), sodium dodecylsulfate (Preparation Example 24), sodium laureth sulfate (Preparation Example 25), cetylpyridinium chloride (CPCl) (Preparation Example 26), α-tocopherol as a synthetic vitamin E derivative (Preparation Example 27), sodium taurocholate (Preparation Example 28), bacteriophages M13, fd, T2, and MS2 (Preparation Examples 29 to 32), or bile acid derivatives represented by Formulas 16 and 17 (Preparation Examples 69 and 70) was dissolved in a solvent shown in Table 3 or 6 with a weight shown in Table 3 or 6, thereby preparing an amphiphilic substance solution. Afterward, the resulting solution was heated to a temperature shown in Table 3 or 6.
Afterward, in Preparation Examples 21, 23 to 27, 29 to 32, 69, and 70, the amphiphilic substance solution was maintained at a temperature shown in Table 3 or 6 for a time shown in Table 3 or 6 to recrystallize, self-assemble or micellize the amphiphilic substance.
The boron nitride dispersion was mixed with the amphiphilic substance solution, and maintained at a temperature shown in Table 3 or 6 for a time shown in Table 3 or 6. As a result, boron nitride scroll composites including an amphiphilic substance inside a boron nitride scroll were obtained.
1.5 g of molybdenum sulfide as a two-dimensional material was added to a solvent shown in Table 4 or 6, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, following sonication for 30 minutes and centrifugation at 4400 rpm for 30 minutes, a molybdenum sulfide dispersion as a supernatant was obtained.
Meanwhile, any one of the amphiphilic substances such as cetyl alcohol (Preparation Example 33), polyoxyethylene-polyoxypropylene (Preparation Example 34), lauroyl microgol glyceride (Preparation Example 35), sodium cholate hydrate (Preparation Example 36), deoxycholic acid (Preparation Example 37), bile acid derivatives represented by Formulas 4 to 8 (Preparation Examples 38 to 42), bacteriophages T2, T4, M13, fd, and P22 (Preparation Examples 43 to 47), and bile acid derivatives represented by Formulas 18 to 20 (Preparation Examples 71 to 73) was dissolved in a solvent shown in Table 4 or 6 with a weight shown in Table 4 or 6, thereby preparing an amphiphilic substance solution. Afterward, the resulting solution was heated to a temperature shown in Table 4 or 6.
Subsequently, in Preparation Examples 34, 35, 38 to 45, and 73, the amphiphilic substance solution was maintained at a temperature shown in Table 4 or 6 for a time shown in table 4 or 6 to recrystallize, self-assemble or micellize the amphiphilic substance.
The molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at a temperature shown in Table 4 or 6 for a time shown in Table 4 or 6. As a result, molybdenum sulfide scroll composites including the amphiphilic substance inside a molybdenum sulfide scroll were obtained.
A molybdenum sulfide dispersion was obtained using the same method as used in Preparation Example 47, except that 1.5 g of molybdenum sulfide was added to dichloromethane.
A bile acid derivative of Formula 7 as an amphiphilic substance and a bacteriophage fd were added to dichloromethane in a weight ratio of 70:30, thereby preparing a solution having a sum concentration of 6 wt %, and the resulting solution was stirred for 0.5 hours, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 55° C.
The molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at room temperature for 24 hours. As a result, a molybdenum sulfide scroll composite including a self assembly of the amphiphilic substance inside a molybdenum sulfide scroll was obtained.
A molybdenum sulfide dispersion was obtained using the same method as used in Preparation Example 47, except that 1.5 g of molybdenum sulfide was added to ODCB.
Cetyl alcohol as an amphiphilic substance and a bacteriophage P22 were added to ODCB in a weight ratio of 50:50, thereby preparing a solution having a sum concentration of 5 wt %, and the resulting solution was stirred for 3 hours, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 120° C.
The molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at 100° C. for 11 hours. As a result, a molybdenum sulfide scroll composite including a self assembly of the amphiphilic substance inside a molybdenum sulfide scroll was obtained.
A molybdenum sulfide dispersion was obtained using the same method as used in Preparation Example 47, except that 1.5 g of molybdenum sulfide was added to chloroform.
An N-hexadecyltrimethylammonium salt as an amphiphilic substance and Al(OH)3 particles as metal oxide particles were added to chloroform in a weight ratio of 70:30, thereby preparing a solution having a sum concentration of 2 wt %, and the resulting solution was stirred for 1 hour, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 40° C., and maintained at room temperature for 18 hours.
The molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at room temperature for 0.1 hours. As a result, a molybdenum sulfide scroll composite including a self assembly of the amphiphilic substance inside a molybdenum sulfide scroll was obtained.
A molybdenum sulfide dispersion was obtained using the same method as used in Preparation Example 47, except that 1.5 g of molybdenum sulfide was added to acetic acid.
Sodium dodecylsulfate as an amphiphilic substance and SiO2 particles as metal oxide particles were added to acetic acid in a weight ratio of 95:5, thereby preparing a solution having a sum concentration of 1 wt %, and the resulting solution was stirred for 4 hours, resulting in an amphiphilic substance solution. Afterward, the amphiphilic substance solution was heated to 70° C., and maintained at −60° C. for 2 hours.
The molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at 250° C. for 0.5 hours. As a result, a molybdenum sulfide scroll composite including a self assembly of the amphiphilic substance inside a molybdenum sulfide scroll was obtained.
1.5 g of graphene/boron carbon nitride (BCN) as a two-dimensional material was added into a solvent shown in Table 5, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, following sonication for 30 minutes and centrifugation at 4400 rpm for 30 minutes, a graphene/boron carbon nitride dispersion as a supernatant was obtained.
Meanwhile, any one of the amphiphilic substances such as sodium laureth sulfate (Preparation Example 52), cetylpyridinium chloride (CPCl) (Preparation Example 53), α-tocopherol as a synthetic vitamin E derivative (Preparation Example 54), sodium taurocholate (Preparation Example 55), and bacteriophages M13, fd, T2, and MS2 (Preparation Examples 56 to 59) was dissolved in a solvent shown in Table 5 with a weight shown in Table 5, thereby preparing an amphiphilic substance solution. Afterward, the resulting solution was heated to a temperature shown in Table 5.
Subsequently, in Preparation Examples 52 to 55, 58, and 59, the amphiphilic substance solution was maintained at a temperature shown in Table 5 and for a time shown in Table 5 to recrystallize, self-assemble or micellize the amphiphilic substance.
The graphene/boron carbon nitride dispersion was mixed with the amphiphilic substance solution, and maintained at a temperature shown in Table 5 and for a time shown in Table 5. As a result, graphene/boron carbon nitride scroll composite materials including an amphiphilic substance inside a graphene/boron carbon nitride scroll were obtained.
1.5 g of graphene/molybdenum sulfide as a two-dimensional material was added to a solvent shown in Table 5, and dispersed by mechanical stirring at 2400 rpm for 1 hour. Afterward, the sonication for 30 minutes and centrifugation at 4400 rpm for 30 minutes, a graphene/molybdenum sulfide dispersion as a supernatant was obtained.
Meanwhile, any one of the amphiphilic substances such as bile acid derivatives represented by Formulas 5 to 8 (Preparation Examples 60 to 63), sodium dodecyl sulfate (Preparation Example 64), and lauryloyl microgol glyceride (Preparation Example 65) was dissolved in a solvent shown in Table 5 with a weight shown in Table 5, thereby preparing an amphiphilic substance solution. Afterward, the resulting solution was heated at a temperature shown in Table 5.
Subsequently, in Preparation Examples 60, 63, and 64, the amphiphilic substance solution was maintained at a temperature shown in Table 5 and for a time shown in Table 5 to recrystallize, self-assemble or micellize the amphiphilic substance.
The graphene/molybdenum sulfide dispersion was mixed with the amphiphilic substance solution, and maintained at a temperature shown in Table 5 for a time shown in Table 5. As a result, graphene/molybdenum sulfide scroll composites including an amphiphilic substance inside a graphene/molybdenum sulfide scroll were obtained.
Any one of the two-dimensional material scroll composites prepared in Preparation Examples 1, 2, 3, 9, 10, 18, 19, 26, 27, 28, 39, 40, 41, 42, 52, 53, 61, and 62 was added to a solvent shown in Table 7, and maintained at a temperature shown in Table 7 for a treatment time shown in Table 7. As a result, the amphiphilic substance contained in the scroll composite was removed, and thus only a hollow scroll remained.
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While Preparation Example 1 and the image (D) use 0.02 mmol of the bile acid derivative of Formula 4, the images (B), (C), and (E) were respectively obtained with mixed solutions of the solutions of the bile acid derivative of Formula 4 obtained with different mole numbers, for example, 0.001 mmol, 0.01 mmol and 0.1 mmol of the bile acid derivative of Formula 4 and the graphene dispersion.
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It is assumed that such G and D phonon shifts of the graphene scroll composite material were caused by the π-π interactions (pi-pi interactions) between scrolled graphene sheets and a morphological change of the graphene scroll.
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As described above, the present invention has been described with reference to exemplary specific preparation examples. However, the scope of the present invention encompasses all of simple modifications or alternations of the present invention, and therefore will be specified by the accompanying claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2014-0025413 | Mar 2014 | KR | national |
| 10-2015-0026298 | Feb 2015 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2015/001976 | 3/2/2015 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/133776 | 9/11/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20080170982 | Zhang | Jul 2008 | A1 |
| 20100009165 | Patel | Jan 2010 | A1 |
| 20130281335 | Altavilla | Oct 2013 | A1 |
| 20150329459 | Blair | Nov 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 102674336 | Sep 2012 | CN |
| 20100025615 | Mar 2010 | KR |
| Entry |
|---|
| Braga et al., Nanoletters 2004, vol. 4(5), 881-884 (Year: 2004). |
| Chen et al. (Nanoscale, 2013, 5, 498-502) (Year: 2013). |
| Da Young Hwang, et al; “Formation of hexagonal boron nitride nanoscrolls induced by inclusion and exclusion of self-assembling molecules in solution process”, Nanoscale; vol. 6, pp. 5686-5690; First published online Apr. 7, 2014. |
| Da Young Hwang, et al: “Inclusion and exclusion of self-assembled molecules inside graphene scrolls and control of their inner-tube diameter”, RSC Adv. vol. 4; pp. 35943-35949; First published online Jul. 2, 2014. |
| Weilang Liang, et al; “Self-Assembly of J-Aggregate Nanotubes and Their Applications for Sensing Dopamine”, Langmuir, 2014, 30(3), pp. 805-811; Publication Date (Web): Jan. 7, 2014. |
| Tiva Sharifi, et al; “Formation of nitrogen-doped graphene nanoscrolls by adsorption of magnetic γ-Fe2O3 nanoparticles”, Nature Communications, Aug. 14, 2013; vol. 4,2319, pp. 1-9. |
| Jian Zheng, et al; “Production of High-Quality Carbon Nanscrolls with Microwave Spark Assistance in Liquid Nitrogen”, Advanced Materials; vol. 23, Issue 21. pp. 2460-2463; First published Apr. 8, 2011. |
| Weiwei Zhou, et al; “Fabrication of Co3O4-Reduced Graphene Oxide Scrolls for High-Performance Supercapacitor Electrodes”, Phys. Chem, Chem. Phys. vol. 13, Issue 32, pp. 14462-14465; First published online Jul. 7, 2011. |
| Weiwei Zhou, et al; Supporting Information for “Fabrication of Co3O4-reduced graphene oxide scrolls for High-Performance Supercapacitor Electrodes”, Phys. Chem. Chem. Phys. vol. 13, Issue 32, 11 pages; First published online Jul. 7, 2011. |
| Shuze Zhu, et al; Hydrogenation enabled scrolling of graphene, Journal of Physics D: Applied Physics; 46; No. 7; Published Jan. 23, 2013; pp. 1-8. |
| International Search Report dated May 29, 2015; PCT/KR2015/001976. |
| Weilang Liang et al; “Self-Assembly of J-Aggregate Nanotubes and Their Applications for Sensing Dopamine”, Langmuir; vol. 30, pp. 805-811; Published Jan. 7, 2014. |
| Number | Date | Country | |
|---|---|---|---|
| 20160355401 A1 | Dec 2016 | US |
