METAL PARTICLE-LOADED HOLLOW MESOPOROUS ORGANOSILICA NANO/MICROPARTICLES AND METHOD FOR MANUFACTURING SAME

Abstract

Disclosed are a hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon, and a method for preparing the same of the present disclosure. The method may prepare a spherical nanoparticle by coating a porous organic silica layer on an inorganic silica particle having the metal particles deposited thereon and via selective etching of the layer. In addition, two or more types of metals pre-synthesized together with a magnetic particle, or different shapes of metals may be deposited on the nanoparticle at a target concentration. Thus, the nano/microparticle may be used for a drug delivery matrix, a catalyst, and a photothermal effect.

Claims

1. A method for preparing a hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon, the method comprising: coating a porous organic silica layer on a surface of an inorganic silica particle having the metal particles deposited thereon; and selectively etching the inorganic silica.

2. The method of claim 1, wherein the inorganic silica particle having the metal particles deposited thereon is prepared by a method including: modifying the surface of the inorganic silica particle with a metal-affinity functional group to prepare an inorganic silica particle having the metal-affinity functional group introduced on the surface of the inorganic silica; attaching the metal particles to the metal affinity functional group to prepare an inorganic silica particle with the metal particles attached thereto; and coating an inorganic silica layer on the inorganic silica particle with the metal particles attached thereto.

3. The method of claim 2, wherein the inorganic silica particle contains magnetic nanoparticles therein.

4. The method of claim 2, wherein the metal-affinity functional group is one of an amine group and a thiol group.

5. The method of claim 2, wherein the inorganic silica is synthesized from tetraethyl orthosilicate (TEOS).

6. The method of claim 2, wherein the metal-affinity functional group is introduced from a member selected from the group consisting of (3-aminopropyl)trimethoxysilane (APTMS), (3-aminopropyl)triethoxysilane (APTES), (3-mercaptopropyl)trimethoxysilane (MPTMS) and (3 -mercaptopropyl)triethoxysilane (MPTES).

7. The method of claim 2, wherein the coating of the inorganic silica layer on the inorganic silica particle with the metal particles attached thereto includes the step of coating the inorganic silica layer to cover all of the metal particles.

8. The method of claim 1, wherein the porous organic silica layer has an open core.

9. The method of claim 1, wherein the coating of the porous organic silica layer is synthesized from solution of an organic silica precursor and a surfactant mixed with each other.

10. The method of claim 9, wherein the organic silica precursor comprises at least one member selected from the group consisting of bis(triethoxysilyl)ethane (BTSE), bis(triethoxysilyl)ethylene (BTSEY), bis-[3-(triethoxysilyl)tetrasulfide] (BTES), bis(triethoxysilyl)phenylene (BTEB), bis(triethoxysilyl)-biphenyl (BTEBP), 1,8-bis(triethoxysilyl)octane (BTEO), bis[3-(triethoxysilyl)propyl] tetrasulfide (BTEPT) and N,N′-bis-[(3-triethoxysilylpropyl)aminocarbonylpolyethylene oxide] (BTEPEO).

11. The method of claim 9, wherein the surfactant comprises at least one member selected from the group consisting of hexadecyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), sodium dodecyl sulfate (SDS), polysorbates and triton.

12. The method of claim 1, wherein the selective etching is performed by heating aqueous solution containing the dispersed inorganic silica particles.

13. The method of claim 1, wherein the selective etching is performed by heating basic aqueous solution containing the dispersed inorganic silica particles.

14. The method of claim 13, wherein a basic component in the basic aqueous solution is selected from the group consisting of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate.

15. A hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon prepared according to claim 1.

16. The hollow mesoporous organic silica nano/microparticle of claim 15, wherein the metal particle includes at least two types of metal particles or includes different shapes of metal particles, and wherein the at least two types of metal particles or the different shapes of metal particles are deposited thereon the hollow mesoporous organic silica nano/microparticle.

17. The hollow mesoporous organic silica nano/microparticle of claim 16, wherein the metal is gold.

18. The hollow mesoporous organic silica nano/microparticle of claim 16, wherein the metal is catalyst metal.

19. The hollow mesoporous organic silica nano/microparticle of claim 16, wherein the nano/microparticle carries a drug.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG. 1 is a view showing a method for preparing a hollow mesoporous organic silica nano/microparticle having metal particles and magnetic nanoparticles deposited thereon.

[0030] FIG. 2 is a scanning electron microscope image of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0031] FIG. 3 is field-emission transmission electron microscopy images of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0032] FIG. 4 is an image showing a XRD pattern of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0033] FIG. 5 is a view showing a nitrogen sorption isotherm and a pore size distribution curve of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0034] FIG. 6 is a view showing magnetic properties of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0035] FIG. 7 shows thermal images of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0036] FIG. 8 is a view showing catalytic reactions of Fe.sub.3O.sub.4/PdNP@YMOM and Comparative Samples prepared according to the present disclosure.

[0037] FIG. 9 is a view showing methods for preparing Sample-1 and Comparative Sample-1 prepared according to the present disclosure.

[0038] FIG. 10 shows TEM images of Sample-1 and Comparative Sample-1 prepared according to the present disclosure.

[0039] FIG. 11 shows TEM images of hollow mesoporous organic silica nano/microparticles having various types of metal particles deposited thereon prepared according to the present disclosure.

[0040] FIG. 12 shows TEM images of a hollow mesoporous organic silica nano/microparticle having metal particles with an increased content deposited thereon.

[0041] FIG. 13 is a view related to a photo-stimulative drug releasing material using a hollow mesoporous organic silica nano/microparticle prepared according to the present disclosure.

[0042] FIG. 14 is a view showing utilization as a tandem micro reactor of a hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon according to the present disclosure.

DETAILED DESCRIPTIONS

[0043] Hereinafter, an embodiment of the present disclosure will be described in detail with reference to the accompanying drawings. The present disclosure may be variously modified and may take many forms. Thus, specific embodiments will be illustrated in the drawings and described in detail herein. However, the specific embodiments are not intended to limit the present disclosure thereto. It should be understood that all changes, equivalents thereto, or substitutes therewith are included in a scope and spirit of the present disclosure. In describing the drawing, similar reference numerals are used for similar components.

[0044] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a” and “an” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or greater other features, integers, operations, elements, components, and/or portions thereof.

[0045] Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Method for Preparing a Hollow Mesoporous Organic Silica Nano/Microparticle Having Metal Particles Deposited Thereon

[0046] The present disclosure provides a method for preparing a hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon.

[0047] FIG. 1 is a view showing a method for preparing a hollow mesoporous organic silica nano/microparticle having metal particles and magnetic nanoparticles deposited thereon. a in FIG. 1 is a schematic diagram of step-by-step preparation of a method for preparing a hollow mesoporous organic silica nano/microparticle having metal particles and magnetic nanoparticles deposited thereon.

[0048] Referring to FIG. 1, the method of preparing the hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon of the present disclosure will be described in detail.

[0049] The method for preparing the hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon includes: coating a porous organic silica layer on a surface of an inorganic silica particle having the metal particles deposited thereon; and selectively etching the inorganic silica. The inorganic silica particle having the metal particles deposited thereon may be prepared by a method including: modifying the surface of the inorganic silica particle with a metal-affinity functional group to prepare an inorganic silica particle having the metal-affinity functional group introduced on the surface of the inorganic silica; attaching the metal particles to the metal affinity functional group to prepare an inorganic silica particle to which the metal particles are attached; and coating an inorganic silica layer on the inorganic silica particle to which the metal particles are attached.

[0050] Specifically, first, the prepared inorganic silica particle is prepared. The inorganic silica particle may be synthesized from tetraethyl ortho silicate (hereinafter, TEOS). In this connection, the inorganic silica particle may contain metal oxide therein. For example, the inorganic silica particle may contain magnetic nanoparticles, and preferably, the magnetic nanoparticles may be Fe.sub.3O.sub.4. The inorganic silica particle containing the metal oxide may be prepared by coating metal oxide nanoparticles with the inorganic silica using an inorganic silica precursor TEOS.

[0051] In order to attach the metal particles to the inorganic silica particle, the surface of the inorganic silica particle is modified with the metal-affinity functional group to prepare the inorganic silica particle onto which the metal-affinity functional group is introduced. The metal-affinity functional group may be one of an amine group and a thiol group, and the metal-affinity functional group may be introduced from one selected from a group consisting of (3-aminopropyl)trimethoxysilane (hereinafter, APTMS), (3-aminopropyl)triethoxysilane (hereinafter, APTES), (3-mercaptopropyl)trimethoxysilane (hereinafter, MPTMS), (3-mercaptopropyl)triethoxysilane (hereinafter, MPTES), and the like as precursors. Preferably, when the metal-affinity functional group is the amine group, the metal-affinity functional group may be introduced from one selected from a group consisting of the (3-aminopropyl)trimethoxysilane (hereinafter, the APTMS) and the (3-aminopropyl)triethoxysilane (hereinafter, the APTES). When the metal-affinity functional group is the thiol group, the metal-affinity functional group may be introduced from one selected from a group consisting of the (3-mercaptopropyl)trimethoxysilane (hereinafter, the MPTMS) and the (3-mercaptopropyl)triethoxysilane (hereinafter, the MPTES).

[0052] The inorganic silica particle to which the metal particles are attached is prepared by attaching the metal particles to the metal-affinity functional group of the inorganic silica onto which the metal-affinity functional group is introduced. The metal particles may be two or more types of metal, or metal particles of different shapes, and the metal particles may be in a form of a nanocube, a nanorod, a nanocage, and the like. As the metal, gold (Au), silver (Au), palladium (Pd), platinum (Pt), and the like may be used. The metal particles may be stirred in aqueous ethanol solution to be attached. For example, a palladium nanocube and a gold nanoparticle may be used as the metal particle.

[0053] The inorganic silica layer is additionally coated on the inorganic silica particle to which the metal particles are attached to prepare the inorganic silica particle having the metal particles deposited thereon. In this connection, the inorganic silica layer may be coated to cover all of the metal particles of the inorganic silica particle to which the metal particles are attached. When the inorganic silica layer is coated to only cover some of the metal particles, it is difficult to prepare a hollow mesoporous organic silica nano/microparticle having spherical metal particles deposited thereon because of exposed metal particles. In addition, the exposed metal particles sink into a mesoporous layer and the shell, which is an interface, in the process of the formation of the mesoporous shell, and are not able to be freely dispersed in an inner cavity of the hollow mesoporous organic silica nano/microparticle having the finally prepared metal particles deposited thereon, so that there is a problem that it is difficult to prepare a mesoporous shell having a high porosity.

[0054] The coating of the inorganic silica layer on the inorganic silica particle to which the metal particles are attached may be essential in preparing the hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon in an independently movable manner. In addition, the inorganic silica layer may be coated through seeded growth. Further, through the above step, the hollow mesoporous organic silica nano/microparticle capable of having various types of metal particles that have already been synthesized deposited thereon may be prepared.

[0055] In one implementation, the inorganic silica layer may be synthesized from the tetraethyl orthosilicate (hereinafter, the TEOS), in the same manner as the inorganic silica particle, and the silica layer may be coated with a seeded growth technique using the TEOS as the precursor.

[0056] A porous organic silica layer is coated on the inorganic silica layer present on the inorganic silica particle having the metal particles deposited thereon. The porous organic silica layer may be synthesized from solution in which an organic silica precursor and a surfactant are mixed with each other. The surfactant is used as a material that guides formation of a meso channel. In one implementation, hexadecyltrimethylammonium bromide (hereinafter, CTAB), cetyltrimethylammonium chloride (hereinafter, CTAC), sodium dodecyl sulfate (SDS), polysorbates, triton, and the like may be used as the surfactant. The organic silica precursor may one or combinations of at least two of bis(triethoxysilyl)ethane (hereinafter, BTSE), bis(triethoxysilyl)ethylene (hereinafter, BTSEY), bis-[3 -(triethoxysilyl)tetrasulfide] (hereinafter, BTES), bis(triethoxysilyl)phenylene (hereinafter, BTEB), bis(triethoxysilyl)-biphenyl (hereinafter, BTEBP), 1,8-bis(triethoxysilyl)octane (hereinafter, BTEO), bis[3-(triethoxysilyl)propyl] tetrasulfide (hereinafter, BTEPT), N,N′-bis-[(3-triethoxysilylpropyl)aminocarbonylpolyethylene oxide] (hereinafter, BTEPEO), and the like. When the BTES, the BTEB, the BTEBP, the BTEO, the BTEPT, the BTEPEO, and the like are used as the organic silica precursor, properties of organic functional groups may be freely controlled by hybridizing various organic functional groups in a silica framework by changing only a type of the organic silica precursor without changing other synthetic protocols. Further, the porous organic silica layer may have an open core.

[0057] The step of selectively etching the inorganic silica may be included after the coating of the porous organic silica layer, thereby preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon. The selective etching may be performed using hydrothermal etching.

[0058] In one implementation, the selective etching may be performed by heating aqueous solution in which the inorganic silica particles are dispersed.

[0059] In another implementation, the selective etching may be performed by heating basic aqueous solution in which the inorganic silica particles are dispersed. In the basic aqueous solution, a basic component may be selected from a group consisting of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate.

[0060] As an example, the inorganic silica prepared using the TEOS is selectively etched using sodium carbonate aqueous solution as the basic aqueous solution based on a difference in a structure of the inorganic silica prepared using the TEOS, which is the inorganic silica precursor, and the porous organic silica layer formed by the CTAB and the BTSE. In addition, the CTAB, which is a meso channel guide material, is removed through ion exchange using ammonium nitrate in the ethanol solution. Thus, the hollow mesoporous organic silica nano/microparticle having the magnetic nanoparticles and/or the metal particles deposited thereon may be finally prepared.

Hollow Mesoporous Organic Silica Nano/Microparticle Having Different Types or Different Shapes of Metal Particles Simultaneously Deposited Thereon

[0061] The hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure may be prepared by the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure.

[0062] In the hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon, the metal may be the two or more types of metal, or the metal particles of the different shapes. The hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon may have the two or more different types of metal, or two or more different shapes of metal deposited thereon. For example, the metal particle may be in the form of the nanocube, the nanorod, the nanocage, and the like. As the metal, the gold (Au), the silver (Au), the palladium (Pd), the platinum (Pt), and the like may be used.

[0063] The hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon of the present disclosure may have not only a narrow size distribution and a high magnetic level, but also the meso channel present in the mesoporous organic silica layer and the hollow inner space. Further, the type of the metal particles may be freely tuned, and the metal particles may be deposited while adjusting a concentration of the metal particles.

[0064] The hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon of the present disclosure having the metal particles and the mesoporous organic silica shell has a wide range of applications such as catalysis, energy storage, and nano medicine.

[0065] In one implementation, in the hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon, the nano/microparticle may carry drug, and the nano/microparticle may be used as a drug carrier. In one implementation, when the metal is the gold in the hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon, the nano/microparticle may be used for photothermal therapy. In one implementation, when the metal is catalyst metal in the hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon, the nano/microparticle may be used as the catalyst.

[0066] Hereinafter, the hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon and the method for preparing the same of the present disclosure will be described in more detail with specific implementations.

EXAMPLE 1

[0067] (1) Synthesis of Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP

[0068] A core-shell Fe.sub.3O.sub.4@SiO.sub.2 composite was prepared using the Stober method. First, ethanol dispersion (35 mL, 1.15 mg/mL) in which Fe.sub.3O.sub.4 is dispersed was put into a 50 mL self-standing falcon tube containing a mixture of 2.5 mL of deionized water and 3 mL of ammonia solution. Thereafter, 4 mL of ethanol solution in which 40 vol % of Tetraethyl orthosilicate (hereinafter, the TEOS) is present was rapidly injected into the mixture, and the mixture was reacted at room temperature for 1 hour while rotating at a speed of 10 rpm. Subsequently, the obtained Fe.sub.3O.sub.4@SiO.sub.2 was filtered and collected, washed several times with the ethanol and the deionized water, and redispersed into 500 mL of deionized water. In order to functionalize a surface of the redispersed Fe.sub.3O.sub.4@SiO.sub.2 with an amino group, (3-aminopropyl)trimethoxysilane (hereinafter, APTMS) (25 mL, 10 vol %) and 5 mL of ammonia solution were added into 500 mL of the Fe.sub.3O.sub.4@ SiO.sub.2 solution, and mechanically stirred at 40° C. for 12 hours to be reacted. Subsequently, Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2 to which the amino group functional group is attached was collected by filtration, washed several times with the ethanol and the deionized water, and re-dispersed again in 40 mL of deionized water. In order to decorate a surface of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2 with AuNP (Au Nano-Particles), after adding aqueous dispersion of AuNP (1 mL, 600 μg/mL) to 5 mL of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2 solution, the mixture was sonicated for 30 minutes and then vigorously stirred for 3 hours to obtain a product. Subsequently, the obtained product was collected by filtration, washed several times with the ethanol and the deionized water, and re-dispersed in 32.5 mL of 1-propanol for a next synthesis procedure, thereby obtaining Fe.sub.3O.sub.4@ SiO.sub.2—NH.sub.2@ AuNP, which is an inorganic silica particle to which a gold particle is attached.

(2) Synthesis of Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2

[0069] Using a seeded silica growth method, the inorganic silica layer was coated on the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP to prepare Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2. Specifically, 32.5 mL of the obtained Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP solution was added into the 50 mL self-standing falcon tube containing the mixture of 2.5 mL of deionized water and 3 mL of ammonia solution. Thereafter, a 0.5 mL solution of 1-propanol in which 20 vol % of TEOS is present was rapidly injected into the mixture, and the mixture was reacted at room temperature for 1 hour while rotating at a speed of 10 rpm to obtain a product. Then, the obtained product was collected by filtration, washed several times with the methanol and the deionized water, and re-dispersed in 20 mL solution in which methanol and aqueous solution exist in 3:7 for a next synthesis procedure, thereby obtaining Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2.

(3) Synthesis of Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2.

[0070] The porous organic silica layer was coated on the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2. Specifically, mixed solution was prepared by mixing 20 mL of the Fe.sub.3O.sub.4@SiO.sub.2. NH.sub.2@AuNP@SiO.sub.2 solution into a 50 mL self-standing falcon tube containing a mixture of 1.4 mL of methanol, 56 mg of CTAB, and 1 mL of ammonia solution. 0.3 mL of methanol solution in which 5 vol % of BTSE is present was rapidly injected into the mixed solution, and reacted at room temperature for 2 hours while rotating at a speed of 10 rpm. Then, the obtained product was collected by filtration, washed several times with the methanol and the deionized water, and re-dispersed in 20 mL of deionized water to obtain Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2@mSiO.sub.2, which is an inorganic silica particle having metal particles coated with the porous organic silica layer deposited thereon.

(4) Synthesis of Fe.sub.3O.sub.4/AuNP@YMOM

[0071] In order to selectively etch non-porous inorganic silica present inside the inorganic silica particle having the metal particles coated with the porous organic silica layer deposited thereon, 20 mL of the solution of Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@AuNP@SiO.sub.2@mSiO.sub.2 obtained above was heated up to 80° C. while being mechanically stirred, then Na.sub.2CO.sub.3 (3 mL, 40 mg/mL), which is basic aqueous solution, was added into 20 mL of the solution of Fe.sub.3O.sub.4@ SiO.sub.2. NH.sub.2@ AuNP@ SiO.sub.2 @ mSiO.sub.2 to form a mixture, and then the mixture is selectively etched. After 1 hour of the etching, a product was obtained. The product was collected by magnet and washed several times with the deionized water. The CTAB, which is the surfactant, was extracted by rapid ion exchange, and treated in ethanol solution (20 mL, 6 mg/mL) in which the ammonium nitrate is present for 3 hours at 60 ° C. Further, in order to completely remove the CTAB, the above process was repeated twice to obtain a surfactant-free product. Finally, the surfactant-free product was collected by the magnet, washed several times with the deionized water, and dried at room temperature for later use, so that the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon according to example 1 of the present disclosure was finally obtained. The obtained hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon was referred to as Fe.sub.3O.sub.4/AuNP@YMOM.

[Property Analysis]

[0072] Analysis on structural properties, structural morphology, and properties of the Fe.sub.3O.sub.4/AuNP@YMOM, which is the hollow mesoporous organic silica nano/microparticles having the metal particles deposited thereon prepared according to Example 1, was performed.

(1) Scanning Electron Microscope Scanning Electron Microscope (SEM) Analysis

[0073] Morphology analysis of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 was performed by a FE-SEM (SUPRA 25, EDAX, carl Zeiss Co, Germany). FIG. 1 shows a result of the morphology analysis.

[0074] FIG. 2 is a scanning electron microscope image of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0075] Referring to FIG. 2, a scale bar in FIG. 2 is 5 μm. In addition, it may be seen that there is a narrow average diameter size distribution of 600 nm.

(2) Field-Emission Transmission Electron Microscopy (FE-TEM) Analysis

[0076] Using a FE-TEM (TALOS F200X, Thermofisher Scientific Co, USA) combined with energy dispersive spectrometry (an energy-dispersive X-RAY, EDX), structural and qualitative elemental analysis on the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 was performed. A result of the structural and qualitative element analysis is shown in FIG. 3.

[0077] FIG. 3 is field-emission transmission electron microscopy images of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0078] First, Referring to a) in FIG. 3, it may be clearly seen that the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure has a shape of a nanoparticle with a hollow structure in which the Fe.sub.3O.sub.4 and multiple AuNPs are uniformly located inside a mesoporous organic silica shell having a thickness of about 40 nm. An image inserted at a top of a) in FIG. 3 is a TEM image of the AuNP used in the preparation of Fe.sub.3O.sub.4/AuNP@YMOM in Example 1. When comparing the TEM image of the AuNP with a TEM image of the Fe.sub.3O.sub.4/AuNP@YMOM of the present disclosure, even when the Fe.sub.3O.sub.4/AuNP@YMOM was prepared by being subjected to a hot water treatment at 80° C. for 1 hour in Na.sub.2CO.sub.3 solution, because a morphological difference from the AuNP or a broken sphere is not observed, it may be seen that the Fe.sub.3O.sub.4/AuNP@YMOM was prepared without damage of the metal particles deposited thereon.

[0079] Referring to b) in FIG. 3, b) is a high-magnification TEM image of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure, and shows that the meso channel is oriented radially in the mesoporous organic silica shell toward a surface of the shell. That is, it may be seen that the Fe.sub.3O.sub.4/AuNP@YMOM has a mesoporous structure with a pore extending vertically from the core. Thus, it may be expected that injection of a guest molecule into an interior space may be preferred.

[0080] Referring to c) in FIG. 3, c) shows EDX elemental mapping images of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure. It may be seen that elements such as Si, Fe, Au, and the like corresponding to a composition of the synthesized material exist, and it may be seen that the hollow mesoporous organic silica nanoparticle having the Fe.sub.3O.sub.4 and the AuNP deposited thereon was prepared.

(3) X-ray Diffractometry (XRD)

[0081] In order to analyze a crystal phase of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure, x-ray diffractometry was performed using an x-ray diffractometer (an xpert3 diffractometer, Malvern Panalytical Ltd, UK) through Cu Kα radiation at 40 kV and 40 mA. A result thereof is shown in FIG. 4.

[0082] FIG. 4 is an image showing a XRD pattern of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0083] Referring to FIG. 4, it may be seen that a diffraction peak of the Fe.sub.3O.sub.4/AuNP@YMOM is clearly distinguished from a diffraction peak of the Fe.sub.3O.sub.4, and it may be seen that characteristic peaks of the Fe.sub.3O.sub.4, the Au, and the silica appear in the diffraction peaks of the Fe.sub.3O.sub.4/AuNP@YMOM. It may be expected that the diffraction peaks of the Fe.sub.3O.sub.4/AuNP@YMOM appear resulted from the deposited Fe.sub.3O.sub.4 and AuNP. Therefore, it may be expected that the Fe.sub.3O.sub.4 and the AuNP are present in the Fe.sub.3O.sub.4/AuNP@YMOM.

(4) Nitrogen Sorption and Pore Size Analysis

[0084] In order to analyze nitrogen sorption and a pore size of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure, a description will be made with reference to FIG. 5.

[0085] FIG. 5 is a view showing a nitrogen sorption isotherm and a pore size distribution curve of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0086] In FIG. 5, it may be seen that the Fe.sub.3O.sub.4/AuNP@YMOM exhibits a type IV curve with a capillary condensation phase, which is a characteristic of a high surface area and a small pore size. A Brunauer-Emmett-Teller (hereinafter, a BET) surface area and a pore volume of the Fe.sub.3O.sub.4/AuNP@YMOM were calculated as 736.63 m2g.sup.−1 and 0.53 cm3g.sup.−1, respectively. It may seen from the pore size distribution graph that meso pores of the organic silica shell are uniform and have an average diameter size of about 2.4 nm.

(5) Magnetic Property Analysis

[0087] A magnetic property of the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure will be described with reference to FIG. 6.

[0088] FIG. 6 is a view showing magnetic properties of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0089] a) in FIG. 6 is a graph from which a magnetic property based on a magnetic field may be identified. It may be seen that a magnetic property graph of the iron magnetic particle Fe.sub.3O.sub.4 and a magnetic property graph of the Fe.sub.3O.sub.4/AuNP@YMOM having the Fe.sub.3O.sub.4 deposited thereon show similar patterns. Thus, it may be seen that the Fe.sub.3O.sub.4/AuNP@YMOM has a magnetic property because of the Fe.sub.3O.sub.4, which is the iron magnetic particles deposited on the nanoparticle. Further, b) in FIG. 6 is a view showing a result of separation using a magnet after dispersing the Fe.sub.3O.sub.4/AuNP@YMOM in a solvent. Referring to b) in 6, it may be seen that the Fe.sub.3O.sub.4/AuNP@YMOM uniformly dispersed in the solvent may be recovered quickly using the magnet. This is an experiment using the magnetic property of the Fe.sub.3O.sub.4/AuNP@YMOM. It may be seen from such experiment that the Fe.sub.3O.sub.4/AuNP@YMOM has the magnetic property.

(6) Photothermal Conversion

[0090] In order to quantitatively evaluate a concentration of the AuNP deposited on the Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure, a photothermal conversion efficiency of the Fe.sub.3O.sub.4/AuNP@YMOM aqueous suspension was measured under 635 nm laser irradiation. The Fe.sub.3O.sub.4/AuNP@YMOM aqueous suspension of a specific concentration was placed in a 200 μL microcentrifuge tube and irradiated with a 635 nm laser for 200 seconds at an output density of 0.55 W/cm.sup.2. A temperature change and an IR image of the sample during the laser irradiation were recorded every 10 seconds using an infrared thermal imaging system (FLIR C3, FLIR Systems Inc, Korea), and a result thereof is shown in FIG. 7.

[0091] FIG. 7 shows thermal images of Fe.sub.3O.sub.4/AuNP@YMOM prepared according to Example 1 of the present disclosure.

[0092] Referring to FIG. 7, rapid heat generation within 70 seconds may be seen from the Fe.sub.3O.sub.4/AuNP@YMOM, so that it may be expected that the temperature increases rapidly under the irradiation with the laser. This proves that the Fe.sub.3O.sub.4/AuNP@YMOM may be applied as a photothermal carrier used in clinical applications of heat generation by the gold nanoparticle.

(7) Catalytic Reaction

[0093] In order to identify a catalytic reaction, FIG. 8 will be referred to.

[0094] FIG. 8 is a view showing catalytic reactions of Fe.sub.3O.sub.4/PdNP@YMOM and Comparative Samples prepared according to the present disclosure.

[0095] A hollow mesoporous organic silica nanoparticle having the palladium metal particles deposited thereon Fe.sub.3O.sub.4/PdNP@YMOM was prepared using a method substantially the same as the preparation method in Example 1 except for using 4 w % of Pd palladium particles as the metal particles.

[0096] Further, Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2, which is a comparative sample, was prepared using a method substantially the same as the preparation method of the Fe.sub.3O.sub.4/PdNP@YMOM except for the step of the selective etching.

[0097] Further, Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP, which is a comparative sample, was prepared using a process substantially the same as the preparation method of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2 except for a step of coating a silica layer on a metal-attached silicon particle and coating a porous organic silica layer on the silica layer.

[0098] a) in FIG. 8 shows TEM images of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP, the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2, and the Fe.sub.3O.sub.4/PdNP@YMOM from the left.

[0099] For the prepared Fe.sub.3O.sub.4/PdNP@YMOM, the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP, and the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2, the catalytic reactions were performed as follows. An aqueous dispersion of the Fe.sub.3O.sub.4/PdNP@YMOMs (10 mL, 10 m/mL) was added to a 50 mL self-standing falcon tube containing NaBH.sub.4 aqueous solution (10 mL, 0.05 M). Then, 4-nitrophenol (hereinafter, 4-NP) aqueous solution (140 μL, 0.01 M) was added thereto and reacted immediately. A UV-vis spectroscopy was used to monitor a change in absorption during the reaction. For comparative studies, the same process was repeated for the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP and the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2, and a result thereof is shown in b) and c) in FIG. 8.

[0100] Referring to b) in FIG. 8, it may be seen that a reduction efficiency of the Fe.sub.3O.sub.4/PdNP@YMOMs is much higher than that of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP and the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2. More specifically, it may be seen in b) that a k value 0.332 min.sup.−1 of the Fe.sub.3O.sub.4/PdNP@YMOMs is about 2.6 times a k value 0.129 min.sup.−1 of the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP, and the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP@SiO.sub.2@mSiO.sub.2 has a value of almost zero because the catalytic reaction does not occur as internal non-porous silica prevents a reactant from reaching a Pd surface.

[0101] It may be expected that an excellent catalytic performance of the Fe.sub.3O.sub.4/PdNP@YMOMs compared to the Fe.sub.3O.sub.4@SiO.sub.2—NH.sub.2@PdNP is mainly due to the Pd palladium particles well dispersed independently in the hollow space. Thus, it may be seen that the Fe.sub.3O.sub.4/PdNP@YMOMs has a high catalytic reaction rate because the Fe.sub.3O.sub.4/PdNP@YMOMs has a much higher catalytic activity surface area. Such result reflects that the uniform vertical meso channels of the organic silica layer facilitate high-rate diffusion and transport of the reactant and the product molecule.

[Comparative Analysis]

[0102] For comparative analysis, Sample-1 of a hollow mesoporous organic silica nanoparticle having the Au and the Fe.sub.3O.sub.4 deposited thereon prepared by the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure was prepared.

[0103] FIG. 9 is a view showing methods for preparing Sample-1 and Comparative Sample-1 prepared according to the present disclosure. The preparation method of Sample-1 will be described with reference to a) in FIG. 9.

[0104] a) in FIG. 9 is a schematic diagram showing the preparation method of Sample-1 prepared using the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure.

[0105] Referring to a) in FIG. 9, Sample-1 was prepared using the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure. Sample-1 was obtained using a method of firstly attaching the metal particles using a metal attachment functional group present on a surface of the silica particle containing the Fe.sub.3O.sub.4, then coating the inorganic silica layer to completely cover the metal particles, then coating the inorganic silica layer with a porous organic silica layer, and then selectively etching the inorganic silica layer.

[0106] Further, in order to compare with this, Comparative Sample-1 of the hollow mesoporous organic silica nanoparticle having the Au and the Fe.sub.3O.sub.4 deposited thereon was prepared. A method for preparing Comparative Sample-1 will be described with reference to b) in FIG. 9.

[0107] b) in FIG. 9 is a schematic diagram showing the preparation method of Comparative Sample-1.

[0108] Referring to b) in FIG. 9, Comparative Sample-1 of the hollow mesoporous organic silica nanoparticle having the Au and the Fe.sub.3O.sub.4 deposited thereon was prepared using a method of attaching the metal particles using the metal attachment functional group present on the surface of the silica particle containing the Fe.sub.3O.sub.4, directly coating the porous organic silica layer without coating the inorganic silica layer to cover the metal, and performing the selectively etching.

[0109] For comparative analysis of Sample-1 and Comparative Sample-1 nanoparticles prepared using different methods, each of which was analyzed using a transmission electron microscopy (TEM). a result thereof is shown in FIG. 10.

[0110] FIG. 10 shows TEM images of Sample-1 and Comparative Sample-1 prepared according to the present disclosure.

[0111] When comparing Sample-1 and Comparative Sample-1 with each other with reference to FIG. 10, it may be seen in a) in FIG. 10 showing Sample-1 of the nanoparticle prepared using the preparation method of the present disclosure that the gold nanoparticles are freely dispersed in the inner cavity without sinking into the mesoporous organic silica shell. On the other hand, it may be seen in b) in FIG. 10 showing Comparative Sample-1 that the gold nanoparticles are sinking or are being fixed at the interior or the interface of the mesoporous organic silica shell, and thus, the gold nanoparticles are not freely dispersed in the defined inner cavity.

[0112] The difference between the nanoparticles prepared using the preparation methods of Sample-1 and Comparative Sample-1 as described above is very important in two aspects. First, when the inorganic nanoparticle used as the catalysts is deposited on the nanoparticle, in the case of the preparation without the coating of the inorganic silica layer for covering the metal as in the preparation method of Comparative Sample-1, because the inorganic nanoparticle sinks and is buried into and present in the mesoporous organic silica layer, a contact area with the reactant is lowered, so that a catalytic activity may be deteriorated or a function as the catalyst may be lost. Second, in the case of the preparation as in the preparation method of Comparative Sample-1, there is a problem that a space in which the inorganic nanoparticle is deposited is limited to an inner surface of the inner cavity. The nanoparticle prepared using the preparation method of the present disclosure has an advantage of dramatically increasing an absolute amount of catalyst that may be deposited because an entirety of the inner cavity becomes a space in which the catalyst may be dispersed.

[Application]

(1) Hollow Mesoporous Organic Silica Nanoparticle Having Various Shapes and Various Types of Metal Particles Deposited Thereon

[0113] In order to identify that the metal is the two or more types of metal or the metal particles of different shapes, and that the at least two different types of metal or the at least two different shapes of metal may be deposited on the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon prepared according to the present disclosure, a description will be made with reference to FIG. 10.

[0114] FIG. 11 shows TEM images of hollow mesoporous organic silica nano/microparticles having various types of metal particles deposited thereon prepared according to the present disclosure.

[0115] Referring to FIG. 11, it may be seen that a) in FIG. 11 is a hollow mesoporous organic silica nanoparticle having spherical gold particles and magnetic nanoparticles deposited thereon, b) is a hollow mesoporous organic silica nanoparticle having nanoroad-shaped gold particles and magnetic nanoparticles deposited thereon, and c) is a hollow mesoporous organic silica nanoparticle having nanocube-shaped gold particles and magnetic nanoparticles deposited thereon. Thus, it may be seen that the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon prepared using the preparation method of the present disclosure may have the metal particles and the magnetic nanoparticles having various shapes deposited thereon.

[0116] d) in FIG. 11 is an image of a hollow mesoporous organic silica nanoparticle having nanocube-shaped palladium and magnetic nanoparticles. It may be seen from d) that not only the gold particles but also various kinds of metal particles may be deposited.

[0117] e) in FIG. 11 shows a composite hollow mesoporous organic silica nanoparticle having not only magnetic nanoparticles and spherical gold nanoparticles, but also a palladium nanocubes simultaneously deposited thereon.

[0118] It may be expected from FIG. 11 that the nanoparticle prepared using the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure is very remarkable in terms of the shape of the deposited metal nanoparticles compared to that prepared using the conventional nanoparticle synthesis method. Thus, it may be seen that various shapes of metal nanoparticles that have already been synthesized may be deposited.

[0119] Further, it was identified that two or more types of metal nanoparticles with different shapes and components may be deposited on the mesoporous layer. Thus, it may be expected that the present disclosure has a very high applicability to a medical field by introducing additional metal nanoparticles capable of performing various functions such as a biocatalytic reaction, an MRI, and the like by depositing not only the gold nanoparticle, but also a metal nanoparticles having a completely different function. Further, the mesoporous organic silica nanoparticle having such metal particles deposited thereon has great significance in enabling complex functions to be implemented in the single nanoparticle structure.

(2) Hollow Mesoporous Organic Silica Nanoparticle Having Metal Particles of an Adjusted Concentration

[0120] In order to identify that the metal particles may be deposited while varying the concentration thereof based on the preparation according to the method for preparing the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure, a description will be made with reference to FIG. 11.

[0121] FIG. 12 shows TEM images of a hollow mesoporous organic silica nano/microparticle having metal particles with an increased content deposited thereon.

[0122] Referring to FIG. 12, it may be identified that the nanoparticle was prepared by increasing the content of the injected metal particles from 0 to 21.95 μmol through the preparation method according to the present disclosure, and an increased amount of metal particles is deposited as an amount of the injected metal increases. Thus, it may be expected that the concentration of the metal particles may be precisely controlled.

(3) Application of Drug Releasing Material

[0123] In addition to the fact that the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure may have various inorganic nanoparticles deposited inside the hollow, because an oil material may be post-encapsulated through the mesoporous organic silica layer, the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon of the present disclosure may be applied as a photo-stimulative drug releasing material of micron to submicron size by combining a photothermal effect of the metal particles and a phase change function based on a temperature of a phase change material (hereinafter, PCM) with each other.

[0124] FIG. 13 is a view related to a photo-stimulative drug releasing material using a hollow mesoporous organic silica nano/microparticle prepared according to the present disclosure. a) in FIG. 13 is a schematic diagram of a preparation process of a photo-stimulative drug releasing material using a hollow mesoporous organic silica nanoparticle prepared according to the present disclosure. b) in FIG. 13 is a diagram showing utilization of a photo-stimulative drug releasing material using a hollow mesoporous organic silica nanoparticle prepared according to the present disclosure.

[0125] Referring to b in FIG. 13, it may be identified that the hollow mesoporous organic silica nanoparticle having the gold particles and the magnetic particles deposited thereon prepared according to the present disclosure may be utilized as the photo-stimulative drug releasing material by encapsulating an anti-cancer substance dissolved in the liquid PCM into the mesoporous organic silica layer through the mesoporous organic silica shell at an elevated temperature of about 60° C., and then cooling the anti-cancer substance at room temperature to change a phase of the PCM to solid. Specifically, because the PCM has the solid phase at about 36° C., which is a human body temperature, even when being injected into cancer cells, the encapsulated anti-cancer substance is not released to the outside through the meso pores. When drug release is necessary, the hollow mesoporous organic silica nanoparticle having the gold particles and the magnetic particles deposited thereon irradiates NIR to increase a temperature of the by about 45° C. or more to change the phase of the PCM to liquid, and thus, allows the internal drug to be released to the outside, so that the hollow mesoporous organic silica nanoparticle having the gold particles and the magnetic particles deposited thereon is utilized as the drug releasing material. When the NIR irradiation is stopped, the phase of the PCM is changed back to the solid as the temperature drops to the body temperature, and thus, the drug release stops. In this way, it may be expected that the hollow mesoporous organic silica nanoparticle having the gold particles and the magnetic particles deposited thereon may be used as the photo-stimulative drug releasing material that may selectively adjust the drug release by irradiating the NIR as needed. In this connection, the magnetic particles that may be selectively deposited may be used in a variety of purposes, such as tracking or visualization of substances through the MRI, recovery using the magnet, or the like.

(4) Utilization of Tandem Micro Reactor

[0126] A fact that the hollow mesoporous organic silica nanoparticle having the metal particles deposited thereon prepared according to the present disclosure may be utilized as a micro reactor in which heterogeneous inorganic catalysts are encapsulated will be described with a specific approach through FIG. 14.

[0127] FIG. 14 is a view showing utilization as a tandem micro reactor of a hollow mesoporous organic silica nano/microparticle having metal particles deposited thereon according to the present disclosure.

[0128] Referring to FIG. 14, it may be identified that the hollow mesoporous organic silica nano/microparticle having the metal particles deposited thereon prepared according to the present disclosure may be used as a tandem catalyst by depositing the heterogeneous inorganic catalysts into one hollow micro-reactor. Therefore, it may be identified that it is possible to construct a microreactor capable of catalyzing two or more chemical reactions in a complementary relationship at a micron level.

[0129] The present disclosure has been described with reference to the preferred embodiments of the present disclosure. Those skilled in the art will understand that the present disclosure may be variously modified and changed without departing from the spirit and scope of the present disclosure as described in the following claims.